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Article history: Three MTW (H-ZSM-12) zeolite samples were synthesized by (i) direct hydrothermal method, (ii) desili-
Received 30 December 2010 cation of the hydrothermal obtained product and (iii) mesostructuration of zeolite ZSM-12 seeds in the
Received in revised form 25 February 2011 presence of hexadecyltrimethylammonium bromide. The samples were characterized by XRD, nitrogen
Accepted 5 March 2011
adsorption isotherms, SEM, 27Al-MAS NMR and FTIR spectroscopy. Their acidity was evaluated by FTIR
Available online 11 March 2011
spectroscopy of CO probe molecule adsorbed at 100 K. The IR results were correlated with the fraction
of aluminum in tetrahedral positions found by 27Al-MAS NMR as well as with the catalytic behavior
Keywords:
toward the transformation of the test molecule of 1,2,4-trimethylbenzene. It was concluded that the den-
ZSM-12
Alkali desilication
sity of the strong Brnsted acid sites, rather than the textural properties, are the dominating factor gov-
Seed mesostructuration erning the catalytic performance of the samples in the target reaction.
Brnsted acidity 2011 Elsevier Inc. All rights reserved.
CO
1387-1811/$ - see front matter 2011 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2011.03.009
292 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
2.2.3. Gas chromatographic pulse injection (GCPI) method 1; 2; 4-TMB wt%F 1; 2; 4-TMB wt%P
X TMB
The GCPI is a method for determination the adsorption capacity 1; 2; 4-TMB wt%F
of hydrocarbons on zeolites and other porous materials [9]. The
L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301 293
CPS
3. Results and discussion 400
b
3.1. Characterization of the samples
200
Some characteristics of the samples studied are shown in Table 1. a
400 7.46
interactions: zeolite mesophase in so-called seed mesostruc- 8.86
tured samples could be found in the review of Perez-Pariente 0
et al. [11]. 300 0 3 6 9
450 consistent with the higher BET specic surface area and the higher
pore volume of desilicated sample.
A However, if the fractional uptake (Ct/C1) is considered, 6.3 min
400
are required to reach 50% of the maximum uptake for the desilicat-
ed sample, while for the parent ZSM-12 zeolite the same uptake is
350
c achieved for 5.3 min (Fig. 3B). The reason for the observed effect
Ads. Volume, STP, cm /g
450
A b 1,0 B
a
Normalized 1,2,4-TMB uptake, a.u. 400
b
350 0,8
a
300
0,6
Ct/C
250
200
0,4
150
100 0,2
50
0,0
0 10 20 30 40 50 60 70 80 0 10 20 30 40 50 60 70 80
Fig. 4. SEM micrographs of the parent H-ZSM-12 zeolite (a), desilicated sample (b) and seed-mesostructured sample (c). The bar corresponds to 1 lm.
A 60.5
B C 60.5
60.5
Intensity, a.u.
Intensity, a.u.
Intensity, a.u.
46.8 4.5
4.5
27
Fig. 5. Solid-state Al-MAS NMR spectra of the starting H-ZSM-12 (a), desilicated H-ZSM-12 (b) and seed-mesostructured H-ZSM-12 (c).
296 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
probe molecules for ne determination of acidity is CO [17,18]. CO A band at 3575 cm1 is also detected with the parent zeolite
forms weak complexes with OH groups and as a result the OH and the desilicated sample. A careful inspection of the spectrum
stretching modes are shifted towards lower frequencies. The high- of the seed mesostructured sample (after automatic background
er the acidity of the hydroxyls, the larger the shift is. The bands correction) indicates a weak intensity band around 3575 cm1 also
corresponding to bridging acidic hydroxyls are usually shifted by with this sample. Assignment of this band is not straightforward.
ca. 300 cm1 [1728] whereas those of isolated silanols, only by Because of its wavenumber, one can stress that it is due to a second
ca. 90 cm1 [1727]. The CO stretching frequencies of OH. . .CO kind of bridging hydroxyls. For instance, FAU type zeolites are
species are also sensitive to the strength of the H-bond formed. characterized by two types of acidic hydroxyls absorbing at ca.
However, they are observed in a relatively narrow spectral region 3650 and 3550 cm1 [17], the 3550 cm1 groups being located at
(21782150 cm1) and are practically not used as a measure for the sodalite cages. Two types of bridging OH groups, at 3612 and
acidity. Note that since the OH. . .CO complexes are unstable, the 3585 cm1 have been detected with H-MOR and attributed to
CO adsorption is performed at low temperature. In this work we hydroxyls in channels and side pockets, respectively [17]. The data
explore the capabilities of CO as an IR probe to characterize three on the hydroxyl groups in ZSM-12 are scarce [16,2932]. Yoo et al.
different H-ZSM-12 samples. [29] reported spectra of high-silica materials that were very differ-
ent from ours because of the low aluminum content. Other authors
[16,30] published IR spectra in the OH region containing two bands
3.2.1. Background spectra assigned to bridging hydroxyls. Unfortunately, the exact frequen-
The FTIR spectra of the activated samples studied are shown in cies were not reported but they seem similar to those we observed.
Fig. 6. The spectrum of the desilicated material (spectrum b) is of Chiche et al. [31] observed two IR bands, at 3609 and 3574 cm1,
good quality while the spectrum of the parent zeolite (spectrum and assigned them to bridging OH groups located in the main
a) is rather noisy. The most intense band for all three samples is channel and in the six- (or eight) membered rings, respectively.
at ca. 3745 cm1. This band is assigned to isolated external silanols The same assignment was adopted in [32] for the bands observed
[17,1927]. The band is most intense with the seed-mesostructured at 3608 and 3574 cm1.
material and of lowest intensity with the parent zeolite. The band at The integral intensity of the bands assigned to acidic hydroxyls
3745 cm1 has a tail towards lower frequencies, which is due to is ca. 2.5 times lower for the desilicated sample as compared with
internal silanols [17,1921,28]. This tail is best pronounced with the parent zeolite. As for the seed-mesostructured sample the
the parent MTW zeolite and shoulders at 3738 and 3725 cm1 are intensity of the band due to acidic hydroxyls is ca. 9 times as low
clearly observed. These results suggest defects in the zeolite bulk as compared with the parent sample.
leading to appearance of internal silanols. A careful inspection of the spectra reveals, for the desilicated
Another band observed with all three samples is located at sample (Fig. 6B, spectrum b), a band of low intensity located
3611 cm1. This band is most intense with the parent zeolite and around 3660 cm1 that was not evident for the other two samples.
appears with reduced intensity in the spectrum of the desilicated This band is assigned to hydroxyls formed with EFAL species
sample (see panel B of Fig. 6). The intensity of this band is very [19,2124,27]. In addition, a broad halo between 3750 and
low with the seed-mesostructured material. In agreement with 3400 cm1 can be distinguished for all samples. This absorbance
many literature data [1727], this band is unambiguously assigned is assigned to H-bonded OH groups probably forming hydroxyl
to zeolite bridging hydroxyls. nests [17].
Since the acidity measurements were performed at low temper-
ature, it is important to note some shift of the OH bands to higher
wavenumbers at 100 K. Thus, the silanol band (3745 cm1) is
A B shifted to 3748 cm1 and the bands of acidic hydroxyls (3611
- 3745
0.05 and 3575 cm1), to 3615 and 357778 cm1, respectively (see
spectra a from Figs. 8, 10 and 13).
0.5
3.2.2. Low temperature CO adsorption on the seed-mesostructured
sample
Because the seed-mesostructured zeolite was characterized by
- 3611
- 3660
ged in concert with the band at 2156 cm1 (Fig. 8, spectra bd and
a Fig. 8, spectra a, c and d). The observed shift of about 90 cm1
a (Dm = 36593748 = 89 cm1) is in agreement with literature data
3800 3600 3600 3500 on the acidity of the silanol groups [1726].
-1 Further evacuation (Fig. 7, spectra df) causes decrease in inten-
Wavenumber, cm sity and disappearance of the band at 2176 cm1 assigned to CO at-
Fig. 6. FTIR spectra of the activated samples: parent zeolite (a), desilicated material
tached to the zeolite acidic hydroxyls [1727]. In agreement with
(b) and seed-mesostructured sample (c). Panel B expands the region of acidic this assignment, we observed a red shift of the band at 3615 to
hydroxyls and spectrum (c) is divided by a factor of two for a better visualization. 3291 cm1 (DmOH = 324 cm1) (Fig. 8, spectra ce). Only at very
L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301 297
2176
2177
2229 2229
- 2176
- 2139
- 2191
- 2139
- 2199
- 2194
2199
f
2135
5
2169
13
- 2156
g
-2
l n
Absorbance
- 2156
2220 2190 2160 2220 2190 2160
Absorbance
- 2176 0.05
0.15
- 2229
- 2229
a a
l n
2250 2200 2150 2100 2250 2200 2150 2100
-1 -1
Wavenumber, cm Wavenumber, cm
Fig. 7. FTIR spectra of CO adsorbed on the seed-mesostructured sample. Equilib- Fig. 9. FTIR spectra of CO adsorbed on the desilicated sample. Equilibrium CO
rium CO pressure of 200 Pa at 100 K (a), 30 Pa at 100 K (b), development of the pressure of 200 Pa at 100 K (a), development of the spectra under dynamic vacuum
spectra under dynamic vacuum at 100 K (cg) and at increasing temperature up to at 100 K (bi) and at increasing temperature up to 293 K (jn). All spectra are
293 K (hl). All spectra are background and gas-phase corrected. background and gas-phase corrected.
- 3748 - 3748
0.1
0.5
- 3659
- 3287
- 3663
Absorbance
- 3572
b
Absorbance
- 3480
- 3400
d
b
- 3291
- 3291
f
e
3615 -
g
3660 -
3577 -
f i
3615 -
a a
high coverages (Fig. 8, spectrum b) the shifted band was detected and, in particular, with the data from a recent paper reporting acid-
at 3285 cm1 due to weak interaction of hydroxyls with more than ity of bridging hydroxyls on H-ZSM-12 (DmOH = 306 cm1) [16].
one CO molecule (solvation effect [20]). The shift of 325 cm1 evi- Difference spectra reveal a shoulder around 3400 cm1 chang-
dences a very high acidity of the bridging hydroxyls. This acidity is ing in synchrony with the band at 3291 cm1. This shoulder is bet-
consistent with many literature data on various zeolites [1727] ter seen with the other two samples because of the higher intensity
298 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
- 3479
that this band is a satellite of the band at 3291 cm1. Indeed, Onida
- 3663
et al. [28] have proposed the complexity of the shifted OH band to a
3290 -
- 3615
be due to the coupling of the OH vibrations with intramolecular
modes. Very recently some of us have provided evidence that the b
appearance of two shifted bands is aroused by Fermi resonance
[33]. 3600 3300
Absorbance
The most stable bands are at 2229 and 2191 cm1 with a shoul-
der at 2199 cm1 (see the inset in Fig. 7). They also disappear upon A 0.05
evacuation, the band at 2229 cm1 being the most resistant one.
- 2176 -
These bands are assigned to carbonyls formed with EFAL species.
Analysis of summarized data on CO adsorption on alumina [18]
indicates that the carbonyl bands at these frequencies are con-
- 2169
nected with coordinative unsaturated tetrahedral aluminum
(c.u.s.) sites.
In conclusion, the seed-mesostructured sample behaves as a
typical zeolite sample with external silanols with low acidity and a
strongly acidic bridging hydroxyls. Lewis acid sites (Al3+) are also
detected. b
- 2176
2229
3
22
- 2192
-2
0.05
2199
g 0.2
- 3660
2220 2190 2160
- 3400
Absorbance
Absorbance
- 2139
d
- 2135
- 2157
- 3291
e
3615 -
- 2161
g
- 2229
a
a
k
2250 2200 2150 2100 3800 3600 3400 3200 3000
-1
Wavenumber, cm Wavenumber, cm
-1
Fig. 12. FTIR spectra of CO adsorbed on the parent sample. Equilibrium CO pressure Fig. 13. Changes in the FTIR spectra in the OH region induced by adsorption of CO
of 200 Pa at 100 K (a), development of the spectra under dynamic vacuum at 100 K on the parent zeolite. Background spectrum registered at 100 K (a), in the presence
(bi) and at increasing temperature up to 293 K (jn). All spectra are background of 100 Pa CO at 100 K (b), and development of the spectra under dynamic vacuum at
and gas-phase corrected. 100 K (cg). Spectra bi corresponds to the spectra ah, respectively, from Fig. 4.
Some spectra are shifted along the Y-axis for clarity.
With this sample the spectra in the OH region are rather nosy Lewis acid sites (Al3+) were also detected in all samples. These
and detailed analysis is hindered. In any case, the shifts of the c.u.s. sites are heterogeneous and probably connected with
silanol band and the bands due to acidic hydroxyls are well de- originally tetrahedral aluminum. They are in highest concentration
tected (Fig. 13). However, the SiOH. . .CO band at 3660 cm1 is with the desilicated sample.
rather broad and has a pronounced low-frequency tail. This allows
us to attribute the carbonyl band at 2161 cm1 and the tail of the 3.2.5. Adsorption of 1,2,4-TMB on desilicated sample
shifted OH band at 3660 cm1 to OH. . .CO species formed with In order to check for the access of 1,2,4-TMB to the OH groups,
internal silanols with enhanced acidity. we have studied the adsorption of this substance on the desilicated
Another peculiarity of the sample is the lack of AlOH species. sample (where the spectrum of the hydroxyl groups was of best
Indeed, it is evident from Fig. 12 that there is no carbonyl band quality). Adsorption of 1,2,4-TMB (equilibrium pressure of
at 2169 cm1 (typical of AlOH. . .CO species). In addition, even 100 Pa) leads to strong decrease in intensity of the silanol bands
small amounts of AlOH species (not visible in the noisy back- at 3745 cm1 and appearance of broader band at 3581 cm1
ground) should produce after CO adsorption an intense shifted (Fig. 14, spectrum a). These results allow assigning the band at
band around 3475 cm1. It is seen from Fig. 13 that no such a band 3581 cm1 to silanols connected to 1,2,4-TMB via H-bond, the in-
was produced. Note that the weak absorbance around this fre- duced shift Dm = 164 cm1. In addition, bands due to adsorbed
quency is typical of the background spectrum. 1,2,4-TMB are seen (for instance the bands in the 3150
Consider now the Al3+ species. A band at 2229 cm1 was regis- 2820 cm1 region).
tered and already assigned to c.u.s. tetrahedral aluminum sites. The The 3581 cm1 band masks the bands due to bridging OH
band at 2223 cm1 evidences another kind of similar species. The groups and does not allow drawing, at this stage, any conclusions
bands below 2200 cm1, also due to aluminum carbonyls, were de- on whether 1,2,4-TMB has affected or not the bands at 3611 and
tected with reduced intensity as compared with the other samples. 3575 cm1. Further evacuation at rt and 373 K leads to decrease
In summary, the parent zeolite sample is characterized by the in intensity of the band at 3581 cm1 until its full disappearance
highest concentration of acidic bridging hydroxyls. Some internal (Fig. 14, spectrum b) and the band at 3746 cm1 (SiOH groups)
silanols with slightly enhanced acidity were also found. In this case is, to a big extent, restored. Simultaneously, the bands characteriz-
again, Lewis acid sites were detected. ing adsorbed 1,2,4-TMB decreases in intensity.
In general, it may be concluded that H-ZSM-12 zeolite is charac- The disappearance of the 3581 cm1 band after evacuation at
terized by two types of acidic bridging hydroxyls, the respective IR 373 K reveals some other peculiarities of the spectra. First, it is
frequencies being at 3611 and 3575 cm1. These two OH groups now well seen that the bands characterizing bridging hydroxyls
are characterized by a high acidity as measured by low-tempera- (3511 and 3575 cm1) and Al-OH groups (3660 cm1) are con-
ture CO adsorption (DmOH of 325 and ca. 295 cm1, respec- sumed and a broad band at 3247 cm1 appeared at their expense.
tively). Desilication leads to a strong (ca. 2/3) decrease in Unfortunately, the shifted band, although showing asymmetry, is
concentration of the Brnsted acid sites. In addition, small amount not well resolved and we can only make the general conclusion
of EFAL species holding AlOH groups is formed. The seed-meso- that the OH modes at 3611 cm1 are red shifted with ca.
structured sample is characterized mainly by one type of Brnsted 365 cm1 upon 1,2,4-TMB adsorption.
acid sites (band at 3611 cm1) in a low concentration (ca. 1/9 of the Secondly, it becomes clear that a broad feature centered at ca.
concentration of the acid sites in the parent zeolite). 3325 cm1 was present in the spectrum recorded under 100 Pa
300 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
3581 -
ples is shown in Fig. 15.
As seen from the gure, the parent ZSM-12 zeolite is more ac-
tive than the desilicated sample in the whole temperature interval
a/2
studied. The seed-mesostructured sample demonstrates the lowest
activity.
Relatively low catalytic activity of desilicated zeolite BEA for li-
Absorbance
- 3247
quid phase benzene alkylation [35] as well as of alkali-treated MFI
zeolite for catalytic cracking of n-octane [36] was also reported in
the literature. The explanation for the reduced activity, according
- 3575
- 3611
100
A 100
B The studied samples show high catalytic conversion and rela-
tively good stability in the reactions of 1,2,4-trimethylbenzene
90 90
transformations. At the experimental conditions studied, the de-
Selectivity to disproportionation, %
Treact.=673 K gree of 1,2,4-TMB conversion seems to be governed by the acid
80
Selectivity to isomerization, %
80
strength and the density of the accessible Brnsted acid sites.
70 70 The acid site density of the desilicated and seed-mesostructured
H-ZSM-12 samples is better tuned for the conduction of selective
60 60
isomerization of 1,2,4-TMB. The microporous H-ZSM-12 zeolite,
50 50 due to its higher acidity, could be more adequate for applications
where disproportionation reactions are preferable.
40 40
30 30 Acknowledgments
References
0 40 80 120 0 40 80 120
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