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Zeolites Al,Na-X and Al,Na-Y with defined numbers of extraframework aluminum cations were prepared
by exchange in an aqueous solution of aluminum nitrate. A maximum concentration of Brnsted acidic bridging
OH groups in supercages (SiOHsupAl) was reached upon dehydration of zeolites Al,Na-X and Al,Na-Y at
423 K. Further raising of the dehydration temperature led to a dehydroxylation of zeolites due to the
recombination of aluminum hydroxyl groups with hydroxyl protons of bridging OH groups. High-field 27Al
multiple-quantum magic-angle spinning (MQMAS) NMR spectroscopy was utilized to study zeolites
Al,Na-X/61 and Al,Na-Y/63 dehydrated at 423 K. Second-order quadrupolar effect parameters of 10.111.0 MHz for tetrahedrally coordinated framework aluminum atoms, compensated in their negative charge
by hydroxyl protons (AlIV/H+) and aluminum cations (AlIV/Alx+), 3.6-4.4 MHz for tetrahedrally coordinated
framework aluminum atoms compensated by sodium cations (AlIV/Na+), and 5.6-7.6 MHz for pentacoordinated
extraframework aluminum cations (Alx+ cat.) were obtained. Comparison of the number of AlOH groups
with the number of pentacoordinated extraframework aluminum cations determined by one-dimensional highfield 27Al MAS NMR spectroscopy gave a ratio near 1:1. This finding and the five-fold coordination of the
cationic extraframework aluminum species hint to the presence of HO-Al+-O-Al+-OH compounds, but
also a minor number of Al(OH)2+ and AlO+ species could exist. The enhanced acid strength of bridging OH
groups in zeolites Al,Na-X and Al,Na-Y in comparison with zeolites H,Na-X and H,Na-Y, as found by
adsorption of acetonitrile, may be due to a polarizing effect of cationic extraframework aluminum species in
the vicinity of Brnsted acid sites.
Introduction
Due to the strongly acidic properties of zeolites, these solid
catalysts are widely used in the hydrocarbon processing
industry.1 In heterogeneously catalyzed reactions, Brnsted and
Lewis acid sites of zeolites play an important role as active
surface sites. Brnsted acid sites acting as proton donors consist
of hydroxyl protons covalently bonded to oxygen atoms bridging
framework silicon and aluminum atoms.2 Lewis acid sites acting
as electron pair acceptors are extraframework species, e.g.,
formed by cation exchange or caused by steaming to create
lattice defects and extraframework aluminum clusters.3 The
change in the distribution of framework aluminum atoms affects
the acid strength of the hydroxyl groups in zeolite. Framework
aluminum atoms with no second-neighbor aluminum atoms are
responsible for strong Brnsted acid sites.4 Moreover, the
presence of multivalent extraframework cations acting as Lewis
acid sites is discussed, as it is thought to play an important role
in the creation of strong Brnsted acid sites in zeolites.
Multivalent lanthanum cations in lanthanum-exchanged zeolites are proposed to influence the framework via a polarizing
or inductive effect, i.e., a withdrawing of electrons from the
framework hydroxyl groups, which leads to an increase of the
strength of the Brnsted acid sites in their vicinity.4-6 Vayssilov
and Rusch reported that charge compensation by alkali or
* Corresponding author. Fax:
michael.hunger@itc.uni-stuttgart.de.
University of Stuttgart.
Universita
t Leipzig.
+49
711
68564081.
E-mail:
Huang et al.
SCHEME 1
Figure 2. 1H MAS NMR spectra of zeolites Al,Na-X/32 (a), Al,Na-X/61 (b), Al,Na-Y/34 (c), and Al,Na-Y/63 (d) dehydrated at 473
and 673 K.
Figure 3. Concentration of bridging OH groups in supercages (SiOHsupAl) and sodalite cages (SiOHsodAl) and of aluminum OH groups (AlOH)
in zeolites Al,Na-X/32 (a) and Al,Na-X/61 (b) plotted as a function
of the dehydration temperature (accuracy (10%). (Al,Na-X/32, 0.0771
mmol u.c. per gram; Al,Na-X/61, 0.0791 mmol u.c. per gram.)
Huang et al.
Figure 4. Concentration of bridging OH groups in supercages (SiOHsupAl) and sodalite cages (SiOHsodAl) and of aluminum OH groups (AlOH)
in zeolites Al,Na-Y/34 (a) and Al,Na-Y/63 (b) plotted as a function
of the dehydration temperature (accuracy (10%). (Al,Na-Y/34, 0.0805
mmol u.c. per gram; Al,Na-Y/63, 0.0819 mmol u.c. per gram.)
SCHEME 2
an additional mechanism must exist leading to a decrease of
the number of AlOH groups. A possible explanation could be
the formation of Al(OH)2+ species in combination with two
SiOHAl groups. In a further step, some of the Al(OH)2+ species
are dehydroxylated to AlO+ under the formation of water
molecules, which is desorbed from the zeolite. Since that total
number of positive charges at the extraframework aluminum
species does not increase in this case, the dehydroxylation of
Al(OH)2+ species is not necessarily accompanied by a dehydroxylation of SiOHAl groups.
2. Accessibility and Acidic Strength of OH Groups in
Al,Na-X and Al,Na-Y Zeolites. To understand the catalytic
function of acid zeolites, it is necessary to consider not only
the number of acid sites but also their accessibility and acid
strength. Therefore, deuterated pyridine (C5D5N) was introduced
as a probe molecule to characterize the accessibility of OH
groups formed in the zeolites.6,21-23 Figure 5 shows the 1H MAS
NMR spectra of dehydrated (473 K) zeolites Al,Na-X/32,
Al,Na-X/61, Al,Na-Y/34, and Al,Na-Y/63 recorded before
and after loading with C5D5N. The assignments of the signals
in the spectra obtained before C5D5N adsorption are the same
as those for the spectra in Figure 2. After adsorption of C5D5N
on dehydrated zeolites Al,Na-X and Al,Na-Y, the accessible
Brnsted acid sites are involved in the protonation of pyridine
to form the pyridinium ions C5D5NH+, which results in a broad
peak at 1H ) 15-16 ppm.6 Simultaneously, the signals of
SiOHAl groups interacting with probe molecules disappeared.
In the case of zeolites Al,Na-X and Al,Na-Y, signals of
SiOHAl groups at 1H ) 3.6-3.9 ppm disappear upon adsorption of deuterated pyridine, which indicates that these hydroxyl
groups are located in the supercages. According to the molecular
diameter of 0.68 nm, pyridine molecules cannot enter the sixring windows of the sodalite cages.
Acetonitrile is a weak base and, therefore, suitable to
discriminate Brnsted sites with different acid strength. Brnsted
sites interact with acetonitrile via O-HN-type hydrogen
bonding. The application of deuterated acetonitrile (CD3CN)
allows 1H MAS NMR studies of Brnsted acid sites without
an overlapping of signals due to a probe molecule. The
resonance shift 1H of the 1H MAS NMR signal of SiOHAl
groups upon adsorption of CD3CN is utilized as a measure of
the acid strength of the corresponding hydroxyl protons.6,24-28
A strong resonance shift corresponds to a high acid strength.
Figure 6 shows the 1H MAS NMR spectra of dehydrated
(473 K) zeolites Al,Na-X/32, Al,Na-X/61, Al,Na-Y/34, and
Al,Na-Y/63 recorded before and after loading with CD3CN.
In the case of zeolites Al,Na-X/32 and Al,Na-X/61, the signals
of bridging OH groups in the supercages shift from 1H ) 3.6
to 7.4 and 8.0 ppm corresponding to 1H values of 3.8 and
4.4 ppm, respectively. Upon adsorption of CD3CN on zeolites
Al,Na-Y/34 and Al,Na-Y/63, this resonance shift 1H is 5.3
ppm in both cases. These adsorbate-induced resonance shifts
1H are lower than those obtained upon adsorption of CD3CN on lanthanum-exchanged zeolites (1H ) 3.8 and 4.9 ppm
for La,Na-X/42 and La,Na-X/75 and 1H ) 5.7 ppm for
Figure 5. 1H MAS NMR spectra of dehydrated (473 K) zeolites Al,Na-X/32 (a), Al,Na-X/61 (b), Al,Na-Y/34 (c), and Al,Na-Y/63 (d)
recorded before (top) and after (bottom) loading with deuterated
pyridine (C5D5N). Asterisks denote spinning side bands.
La,Na-Y/74).6
La,Na-Y/42 and
On the other hand, the
adsorbate-induced resonance shifts 1H observed for zeolites
Al,Na-X and Al,Na-Y are significantly higher than the values
obtained for zeolite X (1H ) 3.6 ppm, see Figure S1,
Supporting Information) and zeolite Y (1H ) 5.1 ppm)25 in
their H forms.
Zeolites X (nSi/nAl ) 1.3) and Y (nSi/nAl ) 2.7) are
characterized by the same framework type (faujasite), but
different framework nSi/nAl ratios. The higher average electronegativity of zeolite Y having the higher framework nSi/nAl
ratio results in a higher acid strength of Brnsted sites in
comparison with those in zeolites X.29 This is the reason for
the higher acid strength of Brnsted sites in zeolites H,Na-Y
(1H ) 5.1 ppm) and Al,Na-Y (1H ) 5.3 ppm) in
comparison with Brnsted sites in zeolites H,Na-X (1H )
3.6 ppm) and Al,Na-X (1H ) 3.8 to 4.4 ppm). In addition,
extraframework cations may enhance the acid strength of
zeolites by affecting the electronegativity of the zeolite framework.29
In the present study, the 1H value was found to increase
with increasing aluminum exchange degree, i.e., for zeolites Al,Na-X/32 and Al,Na-X/61. However, no effect of the aluminum exchange degree on the acid strength of bridging OH
Figure 6. 1H MAS NMR spectra of dehydrated (473 K) zeolites Al,Na-X/32 (a), Al,Na-X/61 (b), Al,Na-Y/34 (c), and Al,Na-Y/63 (d)
recorded before (top) and after (bottom) loading with deuterated
acetonitrile (CD3CN).
Huang et al.
signal
1/ppm
2/ppm
CS/ppm
SOQE/MHz
Al,Na-X/61
1
2
3
4
1
2
3
4
80
64
38
8
80
64
44
10
50
58
30
0
55
60
30
0
69
61
35
5
71
62
39
6
11.0
4.4
5.6
5.6
10.1
3.6
7.6
6.2
Al,Na-Y/63
Figure 7. 27Al MQMAS NMR spectra of dehydrated (473 K) zeolites
Al,Na-X/61 (a) and Al,Na-Y/63 (b).
TABLE 2: Relative Intensities I and Concentration nAl of Aluminum Species in Dehydrated (473 K) Zeolites Al,Na-X/61 and
Al,Na-Y/63 Determined by Simulating the 27Al High-Speed MAS NMR Spectra in Figure 8 (Accuracy of (10%)
signal
1
assignment
AlIV/H+
AlIV/Na+
Al,Na-X/61
(nAl,total ) 100.0)
Al,Na-Y/63
(nAl,total ) 62.9)
AlIV/Alx+
42.9
42.9
47.6
29.9
37.8
37.8
30.8
19.4
I (%)
nAl (Al/u.c.)
I (%)
nAl (Al/u.c.)
3
Alx+
4
cat.
16.9
16.9
18.9
11.9
AlVI
2.4
2.4
2.7
1.7
Huang et al.
(19) Hirschler, A. E. J. Catal. 1963, 2, 428-439.
(20) Guzman, A.; Zuazo, I.; Feller, A.; Olindo, R.; Sievers, C.; Lercher,
J. A. Microporous Mesoporous Mater. 2005, 83, 309-318.
(21) Weihe, M.; Hunger, M.; Breuninger, M.; Karge, H. G.; Weitkamp,
J. J. Catal. 2001, 198, 256-265.
(22) Hunger, M. Solid State Nucl. Magn. Reson. 1996, 6, 1-29.
(23) Hunger, M. Catal. ReV.sSci. Eng. 1997, 39, 345-393.
(24) Jaenchen, J.; van Wolput, J. H. M. C.; van de Ven, L. J. M.; de
Haan, J. W.; van Santen, R. A. Catal. Lett. 1996, 39, 147-152.
(25) Huang, J.; Jiang, Y.; Marthala, V. R. R.; Wang, W.; Sulikowski,
B.; Hunger, M. Microporous Mesoporous Mater. 2007, 99, 86-90.
(26) Simperler, A.; Bell, R. G.; Anderson, M. W. J. Phys. Chem. B
2004, 108, 7142-7151.
(27) Simperler, A.; Bell, R. G.; Foster, M. D.; Gray, A. E.; Lewis, D.
W.; Anderson, M. W. J. Phys. Chem. B 2004, 108, 7152-7161.
(28) Paze`, C.; Zecchina, A.; Spera, S.; Cosma, A.; Merlo, E.; Spano`,
G.; Girotti, G. Phys. Chem. Chem. Phys. 1999, 1, 2627-2629.
(29) Mortier, W. J. J. Catal. 1978, 55, 138-145.
(30) Bhering, D. L.; Ramirez-Solis, A.; Mota, C. J. A. J. Phys. Chem.
B 2003, 107, 4342-4347.
(31) Jiao, J.; Ray, S. S.; Wang, W.; Weitkamp, J.; Hunger, M. Z. Anorg.
Allg. Chem. 2005, 631, 484-490.
(32) Thomas, J. M.; Klinowski, J.; Ramdas, S.; Hunter, B. K.; Tennakoon, D. T. B. Chem. Phys. Lett. 1983, 102, 158-162.
(33) Radeglia, R.; Engelhardt, G. Chem. Phys. Lett. 1985, 114, 28-30.
(34) Rocha, J.; Morais, C. M.; Fernandez, C. Top. Curr. Chem. 2004,
246, 141-194.
(35) Ernst, H.; Freude, D.; Pfeifer, H.; Wolf, I. Stud. Surf. Sci. Catal.
1994, 84, 381-385.
(36) Li, S.; Zheng, A.; Su, Y.; Zhang, H.; Chen, L.; Yang, J.; Ye, C.;
Deng, F. J. Am. Chem. Soc. 2007, 129, 11161-11171.