Characterization of zeolite acidity. II.

Measurement of zeolite acidity by

ammonia temperature programmed
desorption and FTi.r. spectroscopy
techniques
B. M. Lok*, B. K. Marcus and C. L. Angell
Union Carbide Corporation, Tarrytown Technical Center, Tarrytown, New York 10591,
USA
(Received 4 April 1985)

The Ammonia Temperature Programmed Desorption (NH3-TPD) technique has been used to study the
acidity of six zeolite samples. The results indicate that, in general, three desorption peaks are observed.
The three peaks fall in the temperature regions of; less than 473 K, 473-673 K, and higher than 673 K.
The first desorption peak is believed to be associated with physically adsorbed or weakly chemically
adsorbed ammonia molecules; the second peak is NH3 molecules adsorbed on zeolite hydroxyl
groups, and the third peak is associated mainly with dehydroxylation, strong Br6nsted acid sites,
and/or Lewis acid sites. The additional data provided by the FTi.r. enables interpretation of the
NH3-TPD chromatogram obtained by the electronic microbalance.

Keywords: Catalysis; acidity; TPD; FT i.r.

INTRODUCTION are about 11, 15 and 22 kcal mo1-1 respectively.

During the last fifteen years, temperature program-
med ammonia desorption (NH3-TPD) has been used
as a tool to study both Br6nsted and Lewis acid sites in
a catalyst. The method has also been applied to zeolite
catalysts ~-a,la-z0,z2-24. Since ammonia is a strong base
and a relatively small molecule (kinetic diameter of
2.62 /~) with a lone pair of electrons, it can reach
practically all acid sites even those within a zeolite
pore having a six-membered ring opening.
The theory behind the TPD-NH3 experiment was
adapted from that of the flash-filament experiment
used in surface science 9-12. There are two assump-
tions made: first, no readsorption of ammonia takes
place during desorption; second, the ammonia mole-
cules are adsorbed on a homogeneous surface with-
out interactions among adsorbed molecules. These
assumptions presume that all molecules desorb with
the same activation energy. It is assumed that the
intracrystalline zeolite surface is homogeneous, and
the amount of ammonia adsorbed in the experiment
is less than that required for monolayer coverage.
Zeolites A '4, X 14, o f f r e t i t e 6, yi-4.15-'20.24,
mordenite 7"1'~'24 and ZSM-55"a'ls"z2-24 have been stu-
died by the NH3-TPD method. O f these, zeolite Y,
mordenite and ZSM-5 have been studied carefully
and completely. J. Cattanach et al., in their paper I
identify three distinct NH3 desorption peaks for Y
zeolite (8= 10 K min -I) located at 463,573 and 673 K
which correspond to the loss of about 45, 28 and 18
molecules of NH3 per unit cell. T h e apparent
activation energies for desorption obtained by
varying the heating rate from 5 to 20 K per minute,
*To whom all correspondence should be addressed
Dehydroxylation is extremely rapid, and the evolved
HzO produces a sharp peak at about 963 K. They
attribute the first peak to 'physically' sorbed NH~;
they also conclude that a HY form generated at 573 K
can be reconstituted to an NH,~-Y form quantitative-
ly. A. Baranski el al. z'3 further propose that the lower
frequency (3550 cm -l) O H groups located in the
small cages correspond to the higher temperature
peak (673 K) and that the higher frequency (3650
cm -l) O H groups located in the super cages corres-
pond to the lower temperature peak (573 K). Howev-
er, P. Chu 15 assigned the OH groups in the opposite
way.
C. Mirodatos et al. 7 studied mordenite acidity by
the NH3-TPD method. Three desorption peaks were
identified (fi= 10 K min-I). The first peak was found
around 373 K and was assigned to physisorbed
ammonia; a broad, intense peak around 633 K and a
small peak around 923 K were assigned to the 3600
cm -I O H groups and the strong Lewis acid sites,
respectively. The 923 K peak probably also contains
some water molecules evolved from the mordenite
dehydroxylation.
Papers by J. R. Anderson et al. 5, N. Topsoe et al. s
and G. P. Babu et al. Is, studied ZSM-5 type zeolites by
the NH3-TPD method, and three peaks were seen in
each case. The 353 K peak was attributed to weakly
adsorbed molecules on sites on the external surface,
or to the interaction of NH3 molecules with surface
oxides or hydroxyl groups by non-specific hydrogen
bonds or to extraneous material. The 448 K peak was
attributed to chemisorbed molecules. These two
peaks correspond to the 3720-3740 cm -l i.r. bands
of lower acidity hydroxyl groups. The 733 K peak was
attributed to strongly chemisorbed molecules and is

0144-2449186/030185-10 $03.00
© 1986 Butterworth & Co. (Publishers) Ltd ZEOLITES, 1986, Vol 6, May 185
Characterization of zeolite acidity Ih Bo M. Lok et al
partially responsible for the 3600 cm -r i.r. band
which characterizes strong Lewis acid sites.
Typically, three desorption peaks are observed in a
zeolite NH3-TPD chromatogram. However, it can be
seen that these three peaks have been assigned to
physically adsorbed species and species chemisorbed
on zeolite hydroxyl and Lewis acid sites. To correlate
the NH3-TPD-chromatogram data with specific hyd-
roxyl groups, we have developed a new technique
using infrared spectroscopy to monitor the ammonia
desorption process at the temperature maximum of
the NH.3-TPD desorption peaks.
EXPERIMENTAL
A Sartorius electronic microbalance was used for the
TPD studies. The temperature was controlled by a
Thermac 6000 temperature controller with a voltage
limiting setting of 70%. The actual temperature of
the sample was measured by a thermocouple located
inside the sample compartment. In all cases but one, a
small sample compartment was used. The resuhs,
which were signals of both the temperature and the
weight changes, were pre-amplified and then led into
a Bascom-Turner Recorder (Model 8120 Data Cen-
ter) for data storage, processing and plotting.
Samples of - 0 . 5 g of pure zeolite powder" of 20-40
mesh were used in all of the studies. First, the sample
was activated at 623 K under vacuum (~5 IX)
overnight. (Note: no dehydroxylation occurred ira
any of the zeolites below 623 K.) Then 800 Torr
pressure of dry ammonia was introduced and allowed
to equilibrate .with the sample for three hours at
ambient temperature; usually, a constant weight was
reached at this point. The sample was first evacuated
with slow pumping overnight to remove physically
adsorbed NHa; when the pressure was down to
approximately 100 Ix, the sample was evacuated with
fast pumping. A constant, final pressure of 4IX was
reached after 3-4 h of pumping. At that constant
pressure, the amount of weight lost over a time
period of one hour was usually negligible (<0.5 nag
h - I ). The sample was then ready for the TPD study.
(To ensure that no readsorption process occurred
during TPD, the sample was subjected to high
vacuum pumping during the entire TPD run.) For
Table 1 Chemical compositions of tested samples
NH4-Y NH4-Y*
SiO2 49.7 58.9
AI2Oa 17.5 16.2
Na20 (K20) 1.8 0.11
(NH4)20 4.4 3.4
LOI** 25.5 19.1
Si/AI 2.4 3.1
(Na+ +NH4+)/AI 0.66 0.42
Source Linde Linde
LOI** - Loss of weight at 623 K under vacuum. Since 623 K activation is used here, the balance weight represents the residual water
*Mildly steamed and NH4 + ion exchanged
***Grose, R. W., and Flanigen, E. M., US Pat. 4 257 885 (1981)
tData calculated from Na20 and (NH4)zO results
186 ZEOLITES, 1986, Vol 6, May
repeat runs, NHa was introduced at ambient temper-
ature after the first TPD run without rehydration of
the sample.
During the NH3-TPD run, the data were collected
as weight versus temperature with points taken at l0 s
intervals; the maximum number of points per run
was 500. The calculation of the temperature rise (l])
was done by using the data taken only from the
middle portion of the temperature plot; the first and
last 500 seconds were not included in the calculation
of the heat-up rate due to their non-linearity. The
weight data were differentiated with respect to time,
then smoothed and scaled. Finally, the rate of
desorption was plotted against temperature. The
peak maximum temperatures were found from the
data printed out by a Texas Instruments 500 printer.
Permanent storage of both the weight data and the
temperature was done on a floppy disk.
For the i.r. work a FT i.r. spectrometer (Nicolet
Model 7199) was used. A self-supported wafer was
loaded into an i.r. cell 21 which was capable of
evacuation, NH3 loading, and programmed heating.
The sample was first activated at 623 K under
vacuum overnight. (NB: It was assumed that activa-
tion at 623 K under vacuum overnight should
decompose most if not all NH~ in the zeolite.) Then
--750 Torr pressure of dry ammonia was introduced
and allowed to equilibrate with the sample for" a few
hours at ambient temperature. The sample was
evacuated at room temperature overnight to remove
physically adsorbed NH:~ and was then ready for i.r.
study.
Each sample was heated ira vacuum at a rate of ~8.5
K per minute to a specific temperature (see Figures
1-6 for details). The sample was then cooled to
ambient temperature and an i.r. spectrum was taken.
The heat-up and i.r. procedures were repeated two to
three times until the highest specified temperature
was reached, and the final i.r. spectrum was taken.
The selection of the specific temperature at which
the i.r. spectrum was taken was chosen from the
NH,3-TPD chromatogram obtained earlier" and was
the temperature at the end of each NH3-TPD peak.
At that temperature, the ammonia species corres-
ponding to the preceding peak was completely
removed from the adsorption site, and the i.r.
NH4,K-L H-Mordenite NH4-LZ-105*** NH4-ZSM-5
~58.9 73.3 89.0 86.8
16.7 10.3 3.68 2.85
(3.1) 0.32 < 0.02 < 0.02
6.9 - 2.09 1.39
14.8 11.6 6.7 5.4
-3 6.04 20.5 25.8
1.01 - <1.0 t <1.0 t
(K*+NH4+)/AI
This Lab Norton This Lab This Lab
Following
The Teaching
In US Pat.
#3 702 886
 Characterization of zeolite acidity I1: B. M. Lok et al
Table 2 NH3 Temperature programmed desorption results

NH4-Y NH4-Y* NH4,K-L

(repeat)*** (repeat) (repeat) (repeat)***
Sample w t . * * (mg) 384.92 371.95 404.97 401.29 415.02 399.83 426.89 410.60 436.32
NHa loading (mg) 28.62 27.07 21.27 17.11 17.94 20.83 19.17 16.55 15.58
Total wt. lost (rag) 43.20 33.60 24.66 21.61 33.13 22.07 35.45 17.31 35.88
Dehydroxylation t* (mg) 14.58 6.53 3.39 4.50 15.19 1.24 16.28 0.76 20.30
Final temp. (K) 878 900 848 951 953 961 865 874 876
Heat-up rate (~=K min -1) 8.3 8.3 8.7 7.6 9.8 9.0 9.6 (?) 8.7 8.0
No. of peaks observed 3 2 2 2 2 2 3 2 3
Peak maxima (TIn=K) 393 387 -- -- 385 389 376
489 506 586 576 480 474 691 (shoulder) 687
553 -- 705 707 631 (shoulder) 821 -- 803
% Area under the peak #1 N.A. N.A. -- N.A. 17 N.A. 17
#2 55 45 50 67 66
#3 45 55 50 16 17

H-Mordenite NH4-LZ-105 NH4-ZSM-5

(repeat) (repeat) (repeat) (repeat)

Sample w t . * * (rag) 445.85 442.52 447.77 444.85 518.11 516.12 522.03 500.11
NH3 loading (mg) 18.89 19.62 19.96 19.04 13.10 13.22 9.89 10.46
Total wt. lost (mg) 22.15 20.43 25.17 21.39 16.08 14.92 13.42 12.47
Dehydroxylation t* (mg) 3.26 0.81 5.21 2.35 2.98 1.70 3.53 2.01
Final temp. (K) 860 871 880 872 882 870 873 917
Heat-up rate (B=K rain -1) 8.8 9.0 8.4 7.9 9.0 8.8 8.6 8.6
No. of peaks observed 2 2 2 2 3 3 3 3
Peak maxima (TIn=K) 416 404 440 413 415 417 418 419
675 669 691 655 618 601 608 622
m _ 783 746 741 754
% Area under the peak #1 60 56 60 57 50 53 48 48
#2 40 44 40 43 45 45 41 40
#3 - - -- -- 7 2 11 1

N.A. Not analysed due to overlapping of the peaks

t Large sample compartment used
** Sample wt. - after 623 K vacuum activation for fresh sample and after TPD for repeated sample
* * * Sample decomposed substantially after the 1st TPD run
tt The amount cited here could include a small amount NHz not decomposed during 623 K activation under vacuum
overnight

hydroxyl region spectra showed increased intensity of
the hydroxyl group band(s) corresponding to that
particular site.
The materials studied, their chemical compositions
and source or manufacturer are listed in Table 1. The
NH~ form of the zeolites was obtained by refiuxing
10 g of the as-synthesized sample (calcined in the
cases of LZ-105 and ZSM-5) in 100 ml of 10 wt%
NH,IC! solution for one hour followed by washing;
the procedure was repeated twice. The final washing
was carried out until the filtrate was chloride fi'ee.
The sample was then dried at 383 K overnight.
Except for N H . r Y and NH,bK-L, the alkali metal
(Na or K) content in these materials was relatively
low, and the interaction between metal cations and
NH3 molecules can be ignored. The presence of
substantial amounts of either Na cations in the
double-six ring sites of N H . r Y , or K in the cancrinite
cage and double-six ring of NH,bK-L while not
interacting strongly with the NH3 molecules, would
certainly balance in part the framework charge and
reduce the number of sites where ammonia could be
adsorbed.
R E S U L T S AND DISCUSSION
In Table 2, we list the TPD results and include the
activated sample weight, the ammonia loading, the
heat-up rate, the final temperature, the number of
peaks observed, the peak maximum temperatures,
and a rough estimate of the area under each peak.
The peak maximum temperature is related to the
activation energy, and the peak area is related to the
number of acid sites.
The NHa-TPD chromatograms with correspond-
ing i.r. spectra for the molecular sieve materials
studied are shown in Figures 1-6. Figure 7 gives i.r.
spectra of NH,j-Y in the 1200-4000 cm -] wavenum-
ber region.
In Table 3 we list the maximum calculated loading
of NH3 for various samples based on the amount of
aluminium in the material assuming (1) that all
aluminium atoms are in the framework and (2) that
all acid sites are accessible to ammonia molecules.
NH3-TPD Study
NH~ loading
In comparing the actual NH3 loading and the
maximum calculated values, NH4-Y, H-Mordenite,
NH4-LZ-105, and NH4-ZSM-5 all show excessive
NH3 loading (Table 3). This excess amount of
ammonia is clearly physically adsorbed and appears
to be dependent on the Si/Al ratio.
In the case of NH4-Y* and NH4,K-L (Table 3), the
actual NH3 loading is below the maximum calculated
value. This can be explained by (1) the presence of

ZEOLITES, 1986, Vol 6, May 187

Characterization of zeolite acidity I1: B. M. Lok et al
Table 3 NH3 loading comparison
NH4-Y NH4"-Y*
Maximum loading (mg/g)* 65.2 66.1
Actual NHz Loading (mg/g) 74.4 52.5 43.2
NH3/u.c. 53.3 36.9 30.4
AI/u.c. 36.3 47.0
M+/u.c. 9.5 0.5
Physically adsorbed NH3/u.c. 6.5 -- --
% Physically adsorbed, NHsasoftotal NH3 12.2 -- --
*Calculated from Si/AI ratio and cation content
non-framework" aluminium species which do not
adsorb NHa since it is known that NH~-Y* does have
non-framework aluminium, (2) the inaccessibility of
the available acid sites and (3) the small amount of
ammonia left after the activation process.
Dehydroxylation
From the actual weight lost and the NHs loading
data (Table 2), it is clear that during every NHs-TPD
study some extra weight loss occurred; such a loss is
attributable to the dehydroxylation process. The
degree of dehydroxylation varies, with N H , K-L
(3.8---4.7 wt%), and NH4-Y (3.8 wt%) losing substan-
tial amounts and the rest, (NH4-Y*, H-Mordenite,
NH4-LZ-105 and NH4-ZSM-5), losing a small
amount (0.6-1.2 wt%). However, substantial dehyd-
roxylation did occur for one NH4-Y* sample when
the sample was heated to 953 K instead of 873 K.
Reproducibility
To examine the reproducibility of the data, several
samples of the same zeolite material were tested more
than once. The reproducibility of these samples with
respect to NH~ weight loading, number of desorption
peaks, peak positions and the area under each peak,
is rather good (Table 2). In the mordenite case, two
different sample compartments, identical in size,
were used and the resuhs still showed good agree-
ment.
Repeatability
All the samples tested were repeated at least once
without rehydration. In the cases of NH,~,K-L anti
NH4-Y there was a loss of crystallinity after the first
run, and the repeated data were meaningless.
However, it was seen that the decomposed materials
clearly had different TPD-chromatograms than the
crystallographically intact ones.
For H-Mordenite and NH.rZSM-5, the repeata-
bility was good. This indicates that the acid sites of
these materials are thermally stable up to at least
873 K. For LZ-105, the repeatability was good except
for the high temperature peak which seemed to be
gone after the first TPD run. The repeatability for the
NH4-Y* sample in one case was good. However,
when a large sample compartment was used with a
faster heat-up rate (9.5 K min -I) and a higher final
temperature (953 K), the repeatability was poor. It
was evident that substantial dehydroxylation of the
NH4-Y* sample occured at higher temperatures.
Without rehydration of the sites, the repeated N H s -
TPD chromatogram of the NH~-Y* sample should
show some changes.
188 ZEOLITES, 1986, Vol 6, M a y
NH4,K-L H-Mordenite NH4-LZ-105 NH4-ZSM-5
52.3 36.9 13.2 8.9
44.9 35.7 42.4 44.6 25.3 18.9
6.2 4.9 7.4 7.8 8.6 6.7
9.0 6.8 4.5 3.6
1.8 0.3 <0.04 <0.04
- - - - 0.9 1.3 4.1 3.1
-- -- 12.2 16.7 47.7 52.2
N H ~ - T P D chromatogram
By comparing all of the NH:~-TPD-chromatograms
(Figures 1--6), we can classify the TPD peaks into three
regions: the first region covers the temperature range
of <473 K, the second region is fi'om 473 to 673 K
and the last region extends from 673 K up. Most of
tile materials tested, except NH,I-Y*, have three
desorption peaks. NH,,-Y material has both its
second and third peaks in the second region. The rest
of the materials, H-Mordenite, NH,I,K-L, NH4-LZ-
105, NH,rZSM-5, have three peaks occurring in the
above described three regions. NHa-Y* material has
only two desorption peaks which fall in the second
and third regions.
The literature 6'7 has suggested that the peaks that
fall in Ihe first region (<473 K) are caused by
physically adsorbed NH:~ molecules. In our study, the
(NHs+M+)/AI ratio fi)r low Si/AI ratio zeolites (Table
3) is less than or close to one. Therefore, there are
few excess (physically adsorbed) ammonia molecules
to account for the large first TPD peak. A more
reasonable explanation would be that the NH..s
molecules desorbed below 473 K are physically and
weakly chemically adsorbed species. However, for
high silica zeolites (ZSM-5 and LZ-105), the high
NH~/AI ratio (Table 2) indicates a large amount o f
physically adsorbed NH~ molecules. Generally, the
second adsorption peaks are also very high in
intensity. The second adsorption peak temperatures
for all the samples tested occurs in the following
order: N H I - Y (489 K) < N H 4 - Y * (583 K) < L Z - 1 0 5
and ZSM-5 (613 K)<H-Mordenite (673 K)
< N H 4 , K - L (691 K). It has been demonstrated that
the NH~ sites associated with the 2nd TPD peak are
related to some of the i.r. absorption bands observed
in H-Mordenite (3600 c m - 1 band) 7 and H-ZSM-5
(3740 cm-I bantl),~.~.ls
The third NH:rTPD peak has been associated with
Lewis acid sites in one instance 7 and with both
Br6nsted and Lewis acid sites in the other ~. This peak
puts the materials in the following order:
NH,I-Y (553 K) < N H r Y * (703 K) < L Z - 1 0 5 and
ZSM-5(~753 K ) < N H j , K - L ( ~ 8 1 3 K ) < H - M o r d e n i t e
(~923 K). The third peak for H-Mordenite, ahhough
it was not observed here due to the low terminating
temperature, was observed in our earlier studies and
in the literature 7.
The first and second desorption peaks usually
account for most of the NH~ adsorbed; the third
adsorption peak is usually very small in absolute
amount and is believed to be associated with either
very strong Br0nsted or Lewis acid sites and/or
dehydroxylation.
 Characterization of.zeolite acidity Ih B. M. Lok et al

1.8

1.6

1.4.

~ 1.2.

~ 1.0.
0
~
< .8.
.E.

.4.

.2.

o0 , , , , , , , ,J.. , .
57'oo 5~o ' ~ o ' 31'oo ' 57'0o ' 5r;0o ' 3~o ' 3;o0 3700 3500 3300 310e 3700 3500 3300 3100
WAVE NUMBERS
(m) (b) (el (d}

8 tl°w x 5 (a.u.)

Y-62

Figure 1
2

0 i
753 s;3
' 953
J T-K
! i

NH 3 TPD chromatogram and hydroxyl region i.r. spectra NH4-Y. (a) Before NH3 adsorption; (b) NH5 at room temperature; (c)
=

NH3 at 413 K; (d) NH3 at 533 K

.675

.600

.525

.450
z
,375.
0

.225

.150

.075

.000 H3~'oo 3500 3~

WAVENUMBERS
31~00 3zoo 5soo 33oo 513) 57'oo
, 1
3500
i
3300
~ =
3100 37'oo ' 3~oo' ~o' 51'oo
(a) It)) (C) (d}

°wt x 5 (a.u.) t l
Y'82

4.

2.

0 =
513 753 ' 993 ' "PK
Figure 2 NH3 TPD chromatogram and hydroxyl region i.r. spectra of N H 4 - Y * (a) Before NH3 adsorption; (b) NH3 at room temperature;
(c) NH3 at 558 K; (d) NH3 at 848 K

ZEOLITES, 1986, Vol 6, May 189

Characterization of zeolite acidity I1: B. M. Lok et al
Hydroxyl region infrared study
Using the peak termination temperature found in
the NH3-TPD study, full i.r. spectra (1200---4000
cm -l) were run on each of the materials, with the
main area of interest being that portion above 3100
c m - I.
NH4-Y
NH4-Y has three NH,~-TPD peaks located at 393,
489, and 553 K. Two temperatures, 413 and 533 K,
were chosen for NH.3-TPD-i.r. study. Since there was
no complete resolution of the three NH:~-TPD peaks,
the 413 and 533 K points were chosen as minimum
points between the two peaks.
Figure la shows the hydroxyl region i.r. spectrum
of NHa-Y after 16 h of 623 K vacuum activation.
There are two hydroxyl bands located at 3637 and
3543 cm-I and the absorbances are 1.935 and 1.280
respectively. Introduction of NH:~ followed by room
temperature evacuation overnight removes both hyd-
roxyl bands. New bands at 3400 and 3180 cm -1
appear (Figure lb). These new bands presumably are
associated with ammonia or the ammonium ion.
During the heat-up of the NH:~-adsorbed NH.rY to
413 K, a small anaount (~15%) of the 3637 and 3543
cm -I bands is recovered and one of them (3637
cm -l) shifts to 3654 cm -l (Figure lc). Therefore, it is
quite clear that the ammonia molecules desorbed at a
temperature below 413 K are largely physically
and/or weakly chemically adsorbed. The recovery of a
small amount of the hydroxyl bands at 413 K could be
due to the strong overlapping of the 1st and 2nd
NH.3-TPD peaks.
The i.r. spectrum taken after" heating the sample to
533 K (Figure ld), shows almost one hundred percent
recovery of both the 3637 and 3543 cm-l bands and
the disappearance of the 3400 and 3180 cm- i. From
this data, it can be seen that the TPD peak between
413 and 533 K is closely related to ammonia adsorbed
on both the 3637 and 3543 cm -l hydroxyl groups.
The third NH:~-TPD peak at 553 K is believed to be
mainly due to the NH3 molecules adsorbed on Lewis
acid sites and/or dehydroxylation. A band at 3740
cm -I attributable to the surface and terminating
hydroxyl groups is not affected by anamonia.
Very similar conclusions can be reached from the
examination of the 1400-1800 cm -! region of the
spectra (Figure 7). Upon the addition of NH:~, bands
appear at 1670 and 1435 cm -I. The first of these
bands can be assigned to NH~ ions, while the second
is assigned to both NH~ ions and adsorbed NH3
molecules.
Heating to 413 K decreases both bands by very
small amoufits corresponding to the small recovery of
the hydroxyl bands. After" heating to 533 K, the 1670
cm -l band is nearly completely removed, and only a
small band remains at 1435 cm -l. These changes
correspond to the nearly complete recovery of the
hydroxyl groups, as the ammonia adsorbed on both
Br6nsted and Lewis acid sites is removed. The
remainder of the 1435 cm- t band corresponds to the
third NH3-TPD peak and partially or totally repre-
sents the ammonia on Lewis acid sites.
Similar i.r. results and interpretations of the 1400-
1800 cm-~ were noted on the other materials studied.
190 ZEOLITES, 1986, Vol 6, M a y
NH4-Y*
NH4-Y* has two, not well resolved, NH3-TPD
peaks located at 586 and 705 K. Two temperatures,
668 and 848 K, were selected for NH,~-TPD-i.r.
study.
NH4-Y* has two intense hydroxyl bands at 3625
and 3545 cm -I with absorbance of 0.72 and 0.662
respectively (Figure 2a). After" adsorbing ammonia
and after room temperature evacuation overnight
(Figure 2b), two hydroxyl bands appeared at 3685 and
3585 cm -I which are clue to hydroxyl groups inac-
cessible to ammonia. Other new bands at 3390 and
3100 c m - ' (broad) are again associated with NH:~ and
NH~ ions.
The i.r. spectrum (Figure 2c) taken after heating up
to 668 K indicates full recovery of both original
hydroxyl groups. Therefore, the NH:~ that is lost
before 668 K is largely bonded to the zeolite hydroxyl
groups at 3625 and 3545 cm -I. Further heating of
the sample to 848 K (Finite 2d) causes substantial
dehydroxylation.
From these resuhs and from the i.r. 1400-1800
cm -I bands, we can conclude that the NH:~-TPD
peak at 705 K is largely associated with the dehyd-
roxylation process with perhaps a very small portion
attributable to very strong Br6nsted and Lewis acid
sites. The 3740 cm- I band is only slightly affected by
NH:~. It is worth noting that the NHj-Y* sample is
the only sample which did not have a TPD peak below
473 K.
NH4,K-L
The NH3-TPD chromatogram of a fresh N H I,K-L
sample also showed three peaks located at 385, 691
and 821 K. The NH,bK-L sample used in the
NH:~-TPD study was found to lye partially decom-
posed after heating up to 875 K, and the NH:~-TPD-
i.r. study results could be complicated by such a fact.
The hydroxyl region i.r. spectrum of N H b K - L
after 623 K activation shows two peaks (Fi~tre 3a): a
weak band at 3630 cm-J and a very broad band at
3265 cm-I. The 3265 cm-l band represents highly
hydrogen bonded hydroxyl groups. After introduc-
ing NH:~ and overnight evacuation, the band at 3630
cm- l disappears, and the broad band at 3265 cm- J is
covered by an even broader and more intense
ammonia band located at approximately 3100 cm -I
(Figure 3b).
The i.r. spectrum after heating to 433 K is
practically identical to that of the NH:~ loaded, room
temperature evacuated sample (Figure 3c). Thus, the
data implies that the first NH:~-TPD peak does not
relate to zeolite hydroxyl groups. After further
heating to 793 K, the i.r. spectrum returns to the
same state as the original sample except that the
broad band at 3265 cm -~ is somewhat reduced in
intensity (Figure 3d). This loss of intensity is most
likely related to the loss of crystallinity and dehyd-
roxylation. It is thus believed that the second NH3-
TPD peak is related to both zeolytic hydroxyl groups
and the dehydroxylation process. The hydroxyl
group located at 3745 cm- l is only slightly affected by
the introduction of NH3 molecules. The entire band
was regenerated after heating to 793 K.
 Characterization of zeolite acidity Ih B. M. Lok e t al

1.0

0.8
Z
,=

~0.6

0.4

, i , = , i
f f
3700 3500 3300 31'00 37'oo ' 3,~o ' 3:Eo ' 31'oo 3700 3500 3300 3100 3700 3500 3300 3100
WAVENUMBERS
(=) (b) (C) (d)

8 NH4, K-L
T
' 5;3 ' 743 ' ' 993 ' ' T°K
Figure NH3 TPD chromatogram and hydroxyl region i.r. spectra of NH4, K-L. (a) Before NH3 adsorption; (b) NHz at room
3
temperature; (c) NH3 at 433 K; (d) NH3 st 793 K

l
0.6

0.4.

i
,<
0.2.

0.1.

3700 3500 3300 3100 37'0o ' 3~o ' =~oo ' ~1'oo 3700 3500 3300 3100 3700 35(x) 3300 3100
WAVENUMBERS
(a) (u) (c) (d)

l ~ xs(a.)

2-

0 5";3 ' 743 ' ' 993 ' ' T'I(

Figure 4 NH3 TPD chromatogram and hydroxyl region i.r. spectra of H-mordenite. (a) Before NHz adsorption; (b) NH3 at room
temperature; (c) NH3 at 533 K; (d) NH3 at 823 K

ZEOLITES, 1986, Vol 6, May 191

Characterization of zeolite acidity Ih B. M. Lok et al
0.5,

0.4,

0.3
Z

iol
0.1.

, , , , l
=7~o.' ==~o ' ~
i l I I i , , , )
' +I'oo 3700 3500 3300 3100 3700 3500 33C0 3100 37400 35c0 3300 31'00
WAVENUMBERS
(:) (c) (d)

dw
CR
x lO (a.u.)

LZ-105

O-
3700 3500 3300 3100

(el ~. I
Figure 5 NHa TPD chromatogram and hydroxyl region i.r. spectra of I_Z-105. (a) Before NH3 adsorption; (b) NH3 at room temperature;
(c) NHz at 478 K; (d) NH3 at 688 K; (e) NH3 at 873 K
0.5

0.4 t

0.3.
Z

io,i
0.1

3700 3500 334X) 3100 3700 3.500 3300 3100 3700 35O0 3300 3100 3700 3500 331:0 3100
WAVENUMBERS
la) (b) (©) (d)

dw
~ x 10 (a.u.)

8
ZSM-5

6_

4_

2_

, , , , , 0
3700 3500 3300 310Q • Poo' ~:oo' :~oo' 3+'oo
513 753 ' o+3 ' ''r-~
(r) I lel

Figure 6 NH3 TPD chromatogram and hydroxyl region i.r. spectra of ZSM-5. (a) Before NH3 adsorption; (b) NH3 at room temperature;
(c) NH3 at 478 K; (d) NH3 at 688 K; (e) NH3 at 873 K; (f) after rehydration

192 ZEOLITES, 1986,.V01 6, May


40001 u32~--'24'00'
",,--~,,o 1800
' ' 14'~3 I~ 1-0()0
WAVENUMBERS
Figure 7 I.r. spectra for NH4-Y. ( ....... ) Before NH3 adsorption;
( ) NH3 at room temperature; ( ) NH3 at 413 K; (
NHa at 533 K
H-Mordenite
H-Mordenite has three well resolved NH3-TPD
desorption peaks at 416, 675 and 923 K (not shown).
Two temperature points, 533 and 823 K, were chosen
for NH3-TPD FT i.r. study.
There are three types of hydroxyl groups observed
in the i.r. spectrum located at 3740, 3655 and 3613
cm-Z (Figure 4a). After introduction of the NH3 gas
and subsequent room temperature evacuation over-
night, it was found that the existing hydroxyl groups
at 3740 and 3613 cm -~ strongly interact with the
NH~ molecules. However, the hydroxyl band at 3655
cm-I decreases only slightly indicating that this type
of hydroxyl group essentially does not interact with
the NHs molecule.
After heating the sample to 533 K, the band at
3655 cm-t fully recovers, and the intensities of the
broad band(s) near 3275 are reduced slightly (Figure
4c). However, the hydroxyl bands at 3740 and 3613
cm -1 are still missing. Further heating to 823 K
eliminates all new bands which formed as a result of
introducing NH~: meanwhile, the original hydroxyl
bands returned but are reduced in intensity probably
due to dehydroxylation (Figure 4d).
Based on these results, it can be concluded that the
first NH~-TPD peak (below 533 K) corresponds to
physically and/or weakly chemically adsorbed NH3.
T h e second NH,3-TPD peak (between 533 and 823 K)
most likely consists of (1) mainly NH3 molecules
chemisorbed on zeolite hydroxyl groups and (2) small
amounts of water which are the dehydroxylation
product. Examination of the 1430 cm-l band shows
that the third NH~-TPD peak (above 823 K) is not
associated with ammonia adsorbed on the Lewis acid
sites, but is dt~e to the dehydroxylation process. The
hydroxyl groups at 3740 cm-I seem to interact with
the NH3 molecules and are regenerated upon heat-
ing to 823 K.
Characterization of zeolite acidity Ih B. M. Lok et al
High silica zeolites
Both ZSM-5 and LZ-105 have three well resolved
NHs-TPD peaks at 418, 613 and 763 K. Three
temperature points were picked for the i.r. studies:
478, 688 and 873 K.
The i.r. spectrum for LZ-105 shows two bands at
3740 and 3610 cm -~ (Figure5a), and the i.r. spectrum
for ZSM-5 shows two sharp bands at 3740 and 3610
cm -l and a broad band around 3475 cm - t (Figure
6a). Comparison of the two spectra show that the
3740 cm -l band is more intense in ZSM-5 than in
LZ-105 and that the 3610 cm -I band is more intense
for LZ-105 than ZSM-5. (NB: the Si/AI ratio is 20%
lower for LZ-105, Table 1.) After the introduction of
NHs and room temperature evacuation overnight,
both LZ-105 and ZSM-5 completely lose the 3610
cm - t band and a small amount of the 3740 cm -1
band (Figures 5b and 6b). The LZ-105 and ZSM-5 i.r.
spectrum show, that there are two new bands appear-
ing at 3375 and 3280 cm -l.
After evacuating to 478 K, the LZ-105 sample
shows some further changes in its i.r. spectrum. T h e
band at 3280 cm-1 is reduced in intensity and shifts
) to 3230 cm - l , and a very small portion of the 3610
cm- 1 band also reappears (Figure 5c). These changes
are mainly due to the removal of physically adsorbed
NH3. The only change in the ZSM-5 i.r. spectrum is
the reappearance of a small portion of the 3610 cm-!
band (Figure 6c). Therefore, the NHs loss below 528K
for ZSM-5 has to be primarily due to physically
adsorbed NH3.
By further heating the sample to 688 K, the
original spectra for both LZ-105 and ZSM-5 are
regenerated except for a small portion of the band at
3375 cm - t that remains (Figures 5d and 6d). T h e
correlation of the 3610 c m - ' hydroxyl groups with
the second NH3-TPD peak (between 478 and 688 K)
is evident.
Finally, upon heating to 873 K, we find no loss of
hydroxyl groups for LZ-105. Therefore, the third
NH~-TPD peak can be attributed to very strong
Lewis acid sites (Figure 5e). For ZSM-5, we find a
substantial loss of hydroxyl groups from the broad
3475 cm -I band (Figure 6e). These hydroxyl bands
can be regenerated by exposing the sample to
moisture, and we can conclude that the third NH3-
TPD peak of ZSM-5 is largely associated with the loss
of hydroxyl groups. However, we cannot rule out that
a portion of the third NH3-TPD peak of ZSM-5
could be related to Lewis acid sites. (NB: The total
area under the third NH3-TPD peak for ZSM-5 is
about 60% larger than that of LZ-105.). The 3740
cm -l band of ZSM-5 and LZ-105 is minimally
affected.
CONCLUSION
We find that the NHa-TPD and the NHa tempera-
ture programmed i.r. studies provide us with useful
information about the assignment of the different
TPD peaks. For low silicon to aluminium ratio
(Si/AI<10) zeolites, the first NH3-TPD peak (below
473 K) is associated largely with weakly chemisorbed
NH3 molecules. However, for high silica to alumi-
nium ratio (Si/AI>10) zeolites, the first NHs-TPD
ZEOLITES, 1986, Vol 6, May 193
Characterization of zeolite acMity I1: B. M. Lok et al

peak (below 473 K) represents mainly physically 'Proceedings of the 5th International Conference of
Zeolites', (Ed. L. V. C. Rees) Heyden and Son Ltd., London,
adsorbed NH3 molecules. The second NH.~-TPD
1980, p. 382
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molecules adsorbed on zeolite hydroxyl groups. The 70, 41
third NH3-TPD peak is associated with dehydroxyla- 9 Amemomiya, Y. and Cvetanovic, R. J. J. Phys. Chem. 1963,
tion, strong Br6nsted acid sites and/or Lewis acid 67, 144
10 (a) Cvetanovic, R. J. and Amemomiya, Y. Catalysis Rev.,
sites. 1972, 6, 21
(b) Cvetavonic, R. J., presented at ACS National Meeting,
Boston, 1972
ACKNOWLEDGEMENTS 11 Cvetanovic, R. J. and Amemomiya, Y. Catalysis Rev. 1972, 6,
The authors would like to thank Drs. E. M. Flanigen, 21
12 Amemomiya, Y. Chemtech. 1976, 128
R. L. Patton and S. T. Wilson for their review of tile 13 Konvalinka, J. A., Sholten, J. J. F. and Rasser, J. C. J. Catal.
manuscript. 1977, 48, 365
14 Kanazirev, V. and Borisova, N. Zeolites 1982, 2, 23
15 Chu, P. J. Catal. 1976, 43, 346
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194 ZEOLITES, 1986, Vol 6, M a y