Microporous and Mesoporous Materials 143 (2011) 291301

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Microporous and Mesoporous Materials

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Catalytic properties and acidity of ZSM-12 zeolite with different textures

L. Dimitrov a,, M. Mihaylov b, K. Hadjiivanov b, V. Mavrodinova c
a
Institute of Mineralogy and Crystallography, Bulgarian Academy of Sciences, Acad. G. Bonchev str., Bl. 107, 1113 Soa, Bulgaria
b
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., Bl. 11, 1113 Soa, Bulgaria
c
Institute of Organic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev str., Bl. 9, 1113 Soa, Bulgaria

a r t i c l e i n f o a b s t r a c t

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

1. Introduction the high 1,3,5-triisopropylbenzene conversion was mainly as-

For catalytic transformation of relatively large organic mole-
cules on zeolites, the factors inuencing activity and selectivity,
along with improved molecular transport, are appropriate acidity
balance and implementation of steric requirements for intermedi-
ates formation, which often are bimolecular species.
One of the advantageous methods for preparation of zeolites
with improved molecular transport and catalytic properties is their
hierarchical design with formation of mixed micro/mesoporous
material. In this respect controlled alkali desilication leads to a
spectacular mesoporosity development in zeolite ZSM-5, without
distinct modication of the acidic properties [1]. However, because
of the relatively low stability of tetrahedral Al in BEA zeolite, desi-
lication of this material is difcult to be controlled. As a result, pre-
calcination for template removal followed by desilication has a
negative effect on the acidic properties and thereby on the catalytic
performance of the material. Very recently tailored mesoporosity
development in zeolite crystals by simultaneous partial detempla-
tion and desilication, especially convenient for zeolite BEA, was
proposed by Perez-Ramirez et al. [2].
Another approach for design of mixed micromesoporous
materials is mesostructuration of zeolite seeds. Thus, for catalytic
cracking of 1,3,5-triisopropylbenzene, micromesoporous ZSM-5
composite catalyst exhibits a higher catalytic activity as compared
with the conventional microporous ZSM-5 zeolite [3]. In this case,
Corresponding author.
E-mail address: dimitrov@ufscar.br (L. Dimitrov).
signed to improved molecular transport, due to the presence of
the hierarchical porosity of the pore walls.
Ryoo et al. [4] communicated remarkably high resistance to
deactivation of MFI type zeolite with mesoporous/microporous
hierarchical structure as compared with conventional MFI and
mesoporous aluminosilicate MCM-41 in various catalytic reac-
tions, such as isomerization of 1,2,4-trimethylbenzene, cumene
cracking, and liquid phase esterication reaction between benzyl
alcohol and hexanoic acid.
We have previously reported the effect of preparation method
of zeolite BEA on their physicochemical properties and catalytic
performance with organic molecules methanol transformation
[5] and a-pinene isomerisation [6].
In the present work we deal with ZSM-12 zeolites, which
according to IZA nomenclature, have an MTW topology. ZSM-12
is a silica rich zeolite with unidimensional 12-membered ring
channel system and pore openings of 5.7  6.1 [7], which are
slightly larger than that of ZSM-5.
Three different ZSM-12 samples were prepared by (i) direct gel
crystallization in hydrothermal conditions, (ii) desilication of gel-
crystallized sample and (iii) mesostructuration of zeolite seeds in
the presence of hexadecyltrimethylammonium bromide surfac-
tant. The synthesized samples were characterized with XRD,
SEM, nitrogen adsorption measurements, 27Al-MAS NMR and FTIR
spectroscopy of CO adsorbed at 100 K. The catalytic performance in
transformation of a relatively bulky molecule, 1,2,4-trimethylben-
zene, was correlated with physicochemical characteristics of stud-
ied samples.

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. Experimental
2.1. Preparation of the samples
2.1.1. Preparation of the ZSM-12 zeolite
The starting ZSM-12 sample was prepared from gel with the fol-
lowing molar ratios of the reagents [8]: SiO2/Al2O3 = 116; TEAOH/
SiO2 = 0.125; H2O/Al2O3 = 1015; OH/SiO2 = 0.125. The source of tet-
raethyl-ammonium hydroxide (TEAOH) was 20 wt% aqueous solu-
tion (Merck), the silica was 40 wt% SiO2 silica sol (AlusilBulgaria)
and sodium aluminate (Riedel-de Haien, reagent grade). The start-
ing gel crystallized in a Teon lined autoclave at 433 K for 144 h.
The obtained material was centrifuged for separation from the
mother liquids, washed several times with distilled water and
ion-exchanged with 0.1 mol L1 solution of NH4NO3 at 333 K for
3 h using 20 ml of the solution per 1 g of the zeolite. Then the sam-
ple was dried for 24 h at 383 K and calcined in air at 853 K for 6 h
to burn out the non-exchanged TEAOH template. After calcination,
the parent sample was once more ion-exchanged according to the
above-described procedure.
2.1.2. Desilication of the ZSM-12 zeolite
Part of the above-prepared starting ZSM-12 sample was sub-
jected to controlled desilication by alkali treatment. The experi-
mental conditions were selected according to literature data [8]:
desilication at 338 K with 0.2 M sodium hydroxide solution for
30 min and liquid-to-solid ratio of 30. After alkaline desilication,
ammonium ion-exchanged form of desilicated sample was pre-
pared by threefold repeated ion-exchange procedure, described
in previous section.
2.1.3. Preparation of the seed-mesostructured ZSM-12 zeolite
Seed-mesostructured ZSM-12 sample was synthesized from the
same starting gel as the parent zeolite. However, after 60 h (about
the half of the necessary time for complete crystallization at 433 K)
the process of crystallization was interrupted. Then hexadecyltrim-
ethylammonium bromide (CTABr, from Merck) dissolved in addi-
tional quantity of H2O was added to the system with vigorous
stirring. Thus following molar ratios were established in the gel:
SiO2/H2O = 0.037 and SiO2/CTABr = 8.6. The sample was left to
crystallize for another 44 h at 433 K. The obtained precipitate
was ltered, washed, dried, ion-exchanged, calcined and one more
time ion-exchanged, as it was performed for the parent ZSM-12
zeolite.
Hydrogen forms of the samples were prepared by thermal
decomposition of the ammonium exchanged forms.
2.2. Techniques
2.2.1. X-ray diffraction (XRD)
The powder XRD patterns were recorded on a TUR-M62 diffrac-
tometer (Co Ka radiation), equipped with a computer-controlled
HZG-4 goniometer.
2.2.2. Low temperature N2 adsorption
The specic surface area of the samples (SBET) was determined
by Micromeritics ASAP 2010M apparatus, based on the data from
the low-temperature nitrogen adsorption. Before the experiments
the samples were dried and evacuated at 107 Pa. The pore size
distribution (PSD) was determined according to the Brunauer
JoinerHallenda (BJH) method.
2.2.3. Gas chromatographic pulse injection (GCPI) method
The GCPI is a method for determination the adsorption capacity
of hydrocarbons on zeolites and other porous materials [9]. The
procedure consists in introducing of pulses in 2 min interval
through the catalyst bed (0.1 g catalyst). The pulses, consisting of
high-purity N2 ow (60 ml min1), saturated with 1,2,4-trimethyl-
benzene (1,2,4-TMB, from Merck) in a bubble saturator equili-
brated at 317.5 K (partial pressure of adsorbate = 0.9 kPa), are
injected until a steady breakthrough is achieved [10]. The temper-
ature of adsorption is set at 308 K and the adsorbed amount of
1,2,4-TMB is calculated by accumulated difference in the peak
areas of the input pulses and the output signals, registered by on-
line gas chromatograph (HP 5890, Series II) equipped with a FFAP
capillary column and a ame ionization detector.
2.2.4. Scanning electron microscopy (SEM)
The SEM was performed on Philips SEM 515 apparatus, working
at acceleration of 20 kV. Observation of the samples was carried
out after coating them with gold.
2.2.5. Solid-state 27Al-MAS NMR
In order to estimate the effect of the preparation method (direct
hydrothermal synthesis, alkaline desilication and seed-mesostruc-
turation) on aluminum ions coordination, solid-state 27Al-MAS
NMR was applied. The 27Al-MAS NMR spectra were recorded on
a Bruker Advance AV 600 spectrometer. The data were obtained
operating at resonance frequency of 600.13 MHz. The samples
were loaded into 4 mm holder, rotating at 14 kHz. Single pulse of
1 ls, with recycle delay of 0.2 s was applied. For each spectrum
approximately 4096 scans were acquired. The chemical shifts were
referenced to 0.1 M Al(NO3)3 solution. For estimation of the per-
cent of non-tetrahedral aluminum in samples, Gaussian de-convo-
lution of the spectra was performed.
2.2.6. FTIR spectroscopy of low temperature CO adsorption: acidity
evaluation
FTIR spectra were recorded in a transmission mode with a Nico-
let Avatar 360 spectrometer, accumulating 64 scans at a spectral
resolution of 2.0 cm1. Self-supporting pellets (ca. 10 mg cm2)
were prepared from the powdered samples and treated directly
in a purpose-made IR cell allowing measurements at ambient
and low temperatures. The cell was connected to a vacuum-
adsorption apparatus allowing to obtain a residual pressure below
103 Pa. Prior to CO adsorption the samples were pretreated rst in
oxygen (13.3 kPa) for 1 h at 673 K and then in dynamic vacuum for
1 h at the same temperature. All spectra were normalized accord-
ing to the overtone bands. Carbon monoxide (>99.997 purity) was
supplied by Linde AG. It was additionally puried by passing
through a liquid nitrogen trap before adsorption.
2.2.7. Catalytic experiments
The transformation of 1,2,4-trimethylbenzene (kinetic diameter
6.7 ) over the studied samples was used as a catalytic test. The cat-
alytic reaction was performed in a xed-bed ow micro-reactor at
atmospheric pressure at temperatures 573723 K. Fractions of the
H-forms of the samples were pressed, crushed, fractionated to
0.80.2 mm and loaded in the reactor. Before the reaction, the cat-
alysts were activated at 823 K for 3 h under N2 ow (65 ml min1).
Then the catalyst bed was put in contact with a high-purity N2 ow
(60 ml min1) passing through a saturator lled with 1,2,4-TMB
and equilibrated at 317.5 K. At these conditions, 0.9 kPa partial
pressure of 1,2,4-TMB was attained. On-line analysis of the reaction
products was performed using HP-GC equipped with 25 m FFAP
capillary column. Conversion and selectivity during 1,2,4-TMB cat-
alytic transformation were calculated according to the equations:
1; 2; 4-TMB wt%F  1; 2; 4-TMB wt%P
X TMB
1; 2; 4-TMB wt%F
 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301 293

1; 2; 3-TMB wt% 1; 3; 5-TMB wt%P 1200

Siso mol=mol
100  1; 2; 4-TMB wt%P A
P P
TeMBs wt% xylenes wt%P 1000
Sdis mol=mol
100  1; 2; 4-TBM wt%P
where XTMB is the total degree of 1,2,4-TMB conversion, the sub-
800
scripts F and P, respectively, represent the composition of the feed
stream and product stream, Siso is the selectivity to isomerization,
Sdis is the selectivity to disproportionation and TeMBs tetrameth-
600
ylbenzenes.

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

3.1.1. X-ray diffraction (XRD) 0

The XRD powder patterns of the studied samples are shown in
Fig. 1A and B. The parent zeolite possesses very good crystallinity
(Fig. 1, pattern a). After alkali treatment for desilication, the XRD 10 15 20 25 30 35
reections even sharpened (Fig. 1, pattern b). This is probably a re- 2, degree
sult of dissolution of unreacted amorphous silica, which might
have existed in the starting sample. These results are also sup- Fig. 1A. XRD powder patterns of the parent H-ZSM-12 (a) and the desilicated
zeolite (b).
ported by the FTIR spectra of the samples in KBr (not shown here),
where sharper bands in the framework region (4001200 cm1)
are observed for desilicated sample in comparison to the starting
800
and seed-mesostructured ones.
The seed-mesostructured sample shows a relatively disordered B 20
mesostructure of zeolite seeds, demonstrating a shoulder at about 700
2h = 1.65 in its XRD pattern (inset in Fig. 1B), along with relatively
low intensity reections of the parent zeolite ZSM-12. Although 600 CPS x 1000
disordered structure is formed, the role of mesophase is to secure
formation of relatively open structure, preferentially with inter- 10
secting channels, which will greatly reduce the diffusion limita- 500
1.65
tions, especially in the catalytic transformations of relatively
large organic molecules. Additional information on the issue of
CPS

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

3.1.2. Low temperature N2 adsorption measurements 200

The textural properties of the studied samples, determined by
low temperature N2 adsorption measurements, are shown in Table
100
1. As seen, desilication leads to increase of the BET specic surface
area with 25% and the mesopore surface area by ca. 100%. The
seed-mesostructured sample is characterized with specic surface 0
area that is intermediate between the areas of the parent and desi- 10 15 20 25 30 35
licated samples, lowest microporous volume and highest pore 2, degree
volume.
The N2 adsorption isotherms of the parent and desilicated sam- Fig. 1B. XRD powder pattern of the seed-mesostructured H-ZSM-12. The small-
ples, as well as the BJH pore size distribution (calculated from the angle XRD pattern of the same sample is shown in the inset.
desorption branch of the isotherms) are shown in (Fig. 2A and B).

The parent H-ZSM-12 zeolite possesses typical isotherm of a

Table 1 microporous material, while the desilicated sample shows pro-
Textural properties of the materials. nounced hysteresis loop due to capillary condensation, an indica-
Sample Preparation SBET Vmicro Smeso Pore volume at tion of the presence of mesopores. The seed-mesostructured
technique (m2/ (cm3/g) (m2/ p/p0 = 0.98 (cm3/ sample is characterized by type IV isotherm, according to the IU-
g) STP g) g) PAC classication, typical of mesoporous materials.
1 Hydrothermal 294.6 0.112 62 0.18 For this sample, at relative pressures higher than 0.9, a sharp in-
synthesis crease of adsorbed volume is observed due to capillary condensa-
2 Desilication of 1 369.4 0.115 140.8 0.38
tion in the inter-particle pores. The hysteresis observed with the
3 Seed- 302.0 0.076 154 0.646
mesostructuration seed-mesostructured sample is a superposition of H2 and H3 types
of hysteresis [12]. As there is not sharp maximum in the pore size
294 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301

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

could be that the diffusivity inside the crystallites interior of desi-

3

300 licated sample has not been enhanced signicantly, regardless of

the created mesopores. Analogous effect has been described for
250 steamed USY zeolite [1315]. According to Kortunov et al. [13]
b the mesopores in the steamed USY do not form interconnected net-
200 work of channels and, consequently, their presence do not signi-
cantly enhance the intracrystalline diffusion. According to Janssen
150 et al. [14,15] if major part of the mesopores, are present as cavities
on the external surface rather than cylindrical pores, the extent of
accessibility of the micropores and the intracrystalline diffusion,
100
a respectively, should not be enhanced substantially. This was actu-
ally observed for the desilicated sample.
50
3.1.4. Scanning electron microscopy
0 The SEM images of the three samples are shown in Fig. 4. The
0,0 0,2 0,4 0,6 0,8 1,0 SEM micrographs of the parent H-ZSM-12 (Fig. 4, image a) and
p/p0 the desilicated sample (Fig. 4, image b) clearly show aggregates
with dimensions of about 2 lm. Detailed observation of the surface
Fig. 2A. Low temperature N2 adsorptiondesorption isotherm of the parent (a), of the crystals proves smoother surface for the parent zeolite and
desilicated (b) and seed-mesostructured H-ZSM-12 zeolites (c). relatively rougher for the deslilicated sample. At the same time,
the seed-mesostructured sample seems to be organized from smal-
ler globular particles with dimensions of about 150200 nm, form-
0,6 ing aggregates with diameter of about 2 lm (Fig. 4, image c).
B
3.1.5. 27Al-MAS NMR
As seen from Fig. 5, spectrum a, the signal in the 27Al-MAS NMR
spectrum of the parent H-ZSM-12 zeolite consists of only one sym-
- 3.7

metric line positioned at ca. 60 ppm and assigned to aluminum in

0,4 tetrahedral coordination. The spectrum of the desilicated sample
(Fig. 5, spectrum b) contains two lines at about 60 and 0 ppm as-
dV/dlog r, cm /g

signed to aluminum in tetrahedral and octahedral coordination,

3

respectively [16]. In the spectrum of the seed mesostructured

c sample (Fig. 5, spectrum c) two broad and non-symmetric lines
0,2
b mesostructured sample are in octahedral coordination. The amount
0,0
10
BJH pore radius, nm
Fig. 2B. BJH pore size distribution of the starting (a), desilicated (b) and seed-
mesostructured samples (c).
distribution, studied by BJH method, it seems that the textural
mesoporosity in this case prevails the structural one.
3.1.3. Adsorption of 1,2,4-TMB as measured by gas chromatographic
pulse injection (GCPI)
Fig. 3A and B presents the normalized amount and the fractional
uptake of adsorbed 1,2,4-TMB with time for the parent zeolite
ZSM-12 and the desilicated sample. As expected, the plots in
Fig. 3A show higher 1,2,4-TMB uptake in case of the desilicated
sample in comparison to the parent ZSM-12 zeolite which is
centered at about 60 and 0 ppm, respectively, are seen. Deconvolu-
tion indicates the presence of a peak at ca. 47 ppm assigned to
aluminum in distorted tetrahedral coordination.
According to the estimated peak surface areas, about 12% of the
aluminum ions in the desilicated sample and about 10% in the seed-
of aluminum ions in distorted tetrahedral coordination in the
seed-mesostructured sample is estimated to be 28% of all of the alu-
a minum detected by 27Al-MAS NMR. On the base of these ndings, it
can be suggested that the most acidic sample should be the parent
100
H-ZSM-12 zeolite because it contains aluminum only in tetrahedral
coordination. The least acidic material should be the seed-meso-
structured sample, containing aluminum in non-framework
octahedral positions (10%), along with aluminum in distorted tetra-
hedral positions (28%). Thus, the desilicated sample is expected to
possess acidity intermediate between those of the parent zeolite
and the seed-mesostructured sample, as it contains tetrahedral
and about 12% non-framework aluminum, but does not contain
aluminum in distorted tetrahedral positions. These ndings are
conrmed below by the FTIR spectroscopic investigations of low
temperature adsorption of CO on the respective samples.
3.2. FTIR spectroscopy of low temperature CO adsorption: acidity
evaluation
Infrared spectroscopy is a unique technique for selective detec-
tion of Lewis and Brnsted acidity [17,18]. One of the most used
 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301 295

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

Time, min Time, min

Fig. 3. Normalized uptake (A) and fractional uptake Ct/C1 (B) of 1,2,4-TMB as a function of adsorption time at 311 K for the parent ZSM-12 (a) and desilicated sample (b) (Ct
denotes the uptake at time t, C1 is the equilibrium sorption value).

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

100 80 60 40 20 0 -20 100 80 60 40 20 0 -20 80 40 0

, ppm , ppm , ppm

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
forms weak complexes with OH groups and as a result the OH
stretching modes are shifted towards lower frequencies. The high-
er the acidity of the hydroxyls, the larger the shift is. The bands
corresponding to bridging acidic hydroxyls are usually shifted by
ca. 300 cm1 [1728] whereas those of isolated silanols, only by
ca. 90 cm1 [1727]. The CO stretching frequencies of OH. . .CO
species are also sensitive to the strength of the H-bond formed.
However, they are observed in a relatively narrow spectral region
(21782150 cm1) and are practically not used as a measure for
acidity. Note that since the OH. . .CO complexes are unstable, the
CO adsorption is performed at low temperature. In this work we
explore the capabilities of CO as an IR probe to characterize three
different H-ZSM-12 samples.
3.2.1. Background spectra
The FTIR spectra of the activated samples studied are shown in
Fig. 6. The spectrum of the desilicated material (spectrum b) is of
good quality while the spectrum of the parent zeolite (spectrum
a) is rather noisy. The most intense band for all three samples is
at ca. 3745 cm1. This band is assigned to isolated external silanols
[17,1927]. The band is most intense with the seed-mesostructured
material and of lowest intensity with the parent zeolite. The band at
3745 cm1 has a tail towards lower frequencies, which is due to
internal silanols [17,1921,28]. This tail is best pronounced with
the parent MTW zeolite and shoulders at 3738 and 3725 cm1 are
clearly observed. These results suggest defects in the zeolite bulk
leading to appearance of internal silanols.
Another band observed with all three samples is located at
3611 cm1. This band is most intense with the parent zeolite and
appears with reduced intensity in the spectrum of the desilicated
sample (see panel B of Fig. 6). The intensity of this band is very
low with the seed-mesostructured material. In agreement with
many literature data [1727], this band is unambiguously assigned
to zeolite bridging hydroxyls.
A B
- 3745
0.5
Absorbance
- 3660
c bands at 2139 and 2135 cm1 are due to physically adsorbed CO
- 3611
- 3575
b to CO polarized by the silanol groups [1726]. Indeed, upon CO
- 3738
3743
3725 -
a Fig. 8, spectra a, c and d). The observed shift of about 90 cm1
3800 3600
Wavenumber, cm
Fig. 6. FTIR spectra of the activated samples: parent zeolite (a), desilicated material
(b) and seed-mesostructured sample (c). Panel B expands the region of acidic
hydroxyls and spectrum (c) is divided by a factor of two for a better visualization.
A band at 3575 cm1 is also detected with the parent zeolite
and the desilicated sample. A careful inspection of the spectrum
of the seed mesostructured sample (after automatic background
correction) indicates a weak intensity band around 3575 cm1 also
with this sample. Assignment of this band is not straightforward.
Because of its wavenumber, one can stress that it is due to a second
kind of bridging hydroxyls. For instance, FAU type zeolites are
characterized by two types of acidic hydroxyls absorbing at ca.
3650 and 3550 cm1 [17], the 3550 cm1 groups being located at
the sodalite cages. Two types of bridging OH groups, at 3612 and
3585 cm1 have been detected with H-MOR and attributed to
hydroxyls in channels and side pockets, respectively [17]. The data
on the hydroxyl groups in ZSM-12 are scarce [16,2932]. Yoo et al.
[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
assigned to bridging hydroxyls. Unfortunately, the exact frequen-
cies were not reported but they seem similar to those we observed.
Chiche et al. [31] observed two IR bands, at 3609 and 3574 cm1,
and assigned them to bridging OH groups located in the main
channel and in the six- (or eight) membered rings, respectively.
The same assignment was adopted in [32] for the bands observed
at 3608 and 3574 cm1.
The integral intensity of the bands assigned to acidic hydroxyls
is ca. 2.5 times lower for the desilicated sample as compared with
the parent zeolite. As for the seed-mesostructured sample the
intensity of the band due to acidic hydroxyls is ca. 9 times as low
as compared with the parent sample.
A careful inspection of the spectra reveals, for the desilicated
sample (Fig. 6B, spectrum b), a band of low intensity located
around 3660 cm1 that was not evident for the other two samples.
This band is assigned to hydroxyls formed with EFAL species
[19,2124,27]. In addition, a broad halo between 3750 and
3400 cm1 can be distinguished for all samples. This absorbance
is assigned to H-bonded OH groups probably forming hydroxyl
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
shifted to 3748 cm1 and the bands of acidic hydroxyls (3611
0.05 and 3575 cm1), to 3615 and 357778 cm1, respectively (see
spectra a from Figs. 8, 10 and 13).
3.2.2. Low temperature CO adsorption on the seed-mesostructured
sample
Because the seed-mesostructured zeolite was characterized by
- 3611
the simplest spectrum in the OH region, we shall start the discus-
sion of the CO adsorption results with this material. Adsorption of
- 3575
c/2 CO (200 Pa) at 100 K on the activated sample provokes appearance
of carbonyl bands at 2229, 2176, 2156, 2139 and 2135 cm1 (Fig. 7,
spectrum a). Broad feature around 2195 cm1 is also visible. The
[18] and disappear easily upon evacuation even at 100 K (Fig. 7,
b spectra bd). A band at 2156 cm1, slightly more stable, is assigned
adsorption the SiOH band at 3748 cm1 was eroded and a new,
broader band at 3659 cm1 appeared (Fig. 8, spectrum b) and chan-
ged in concert with the band at 2156 cm1 (Fig. 8, spectra bd and
a (Dm = 36593748 = 89 cm1) is in agreement with literature data
3600 3500 on the acidity of the silanol groups [1726].
-1 Further evacuation (Fig. 7, spectra df) causes decrease in inten-
sity and disappearance of the band at 2176 cm1 assigned to CO at-
tached to the zeolite acidic hydroxyls [1727]. In agreement with
this assignment, we observed a red shift of the band at 3615 to
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

3800 3600 3400 3200 3800 3600 3400 3200

-1
Wavenumber, cm
Fig. 8. Changes in the FTIR spectra in the OH region induced by adsorption of CO on
the seed-mesostructured sample. Background spectrum registered at 100 K (a), in
the presence of 200 Pa CO at 100 K (b), and development of the spectra under
dynamic vacuum at 100 K (cf). Spectra bf correspond to the spectra a, c, d, e and g,
respectively, from Fig. 2. Some spectra are shifted along the Y-axis for clarity.
-1
Wavenumber, cm
Fig. 10. Changes in the FTIR spectra in the OH region induced by adsorption of CO
on the desilicated sample. Background spectrum registered at 100 K (a), in the
presence of 200 Pa CO at 100 K (b), and development of the spectra under dynamic
vacuum at 100 K (ci). Spectra bi corresponds to the spectra ah, respectively,
from Fig. 4. Some spectra are shifted along the Y-axis for clarity.

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
of the bands (see below). Some researchers have assigned such a
shoulder to heterogeneity of the hydroxyls [20,21] but it seems
that this band is a satellite of the band at 3291 cm1. Indeed, Onida
et al. [28] have proposed the complexity of the shifted OH band to
be due to the coupling of the OH vibrations with intramolecular
modes. Very recently some of us have provided evidence that the
appearance of two shifted bands is aroused by Fermi resonance
[33].
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
evacuation, the band at 2229 cm1 being the most resistant one.
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-
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
strongly acidic bridging hydroxyls. Lewis acid sites (Al3+) are also
detected.
3.2.3. Low temperature CO adsorption on desilicated sample
The next sample we shall consider is the desilicated one be-
cause of the restricted noise in the OH region as compared with
the parent zeolite. The carbonyl spectrum registered after adsorp-
tion of CO (300 Pa, 100 K) on the activated sample is shown in
Fig. 9, spectrum a. Bands at 2229, 2194, 2177, 2169, 2156, 2139
and 2135 cm1 are detected. The changes in the OH region induced
by CO adsorption are more complex as compared with the seed-
mesostructured sample: bands at 3663, 3572, 3483, 3400 and
3287 cm1 are detected after CO adsorption (Fig. 10, spectrum b).
Evacuation leads to fast disappearance of the physically ad-
sorbed CO (2139 and 2135 cm1) and CO attached to external sila-
nols (2156 cm1) (Fig. 9, spectra bd). A band at 3660 cm1 was
found to correlate with the 2156 cm1 band. The stability of the
other carbonyls bands increases with their wavenumber. At low
coverages (see the inset in Fig. 9) Al3+CO bands are detected at
2229, 2199 and 2194 cm1.
In this case again, the band at 3615 cm1 is shifted by about
325 cm1, to 3291 cm1. A satellite of this band is well observed
at 3400 cm1 (Fig. 10).
The carbonyl band at 2169 cm1 correlates with the OH. . .CO
band around 3480 cm1. Difference spectra reveal parallel disap-
pearance of a band at 3663 cm1 (see the inset, Fig. 11). Note that
this band coincides with position with the SiOH. . .CO band but is
affected by CO at different coverages. On this basis and in agree-
ment with literature data [18,19,22,24], we assign the band at
2169 cm1 to CO attached to AlOH groups. The observed shift of
the OH modes by about 185 cm1 is in good agreement with pub-
lished data [22,33].
Let us now discuss the band at 3577 cm1 present in the back-
ground spectrum and assigned to Brnsted sites (Fig. 10, spectrum
a). To help evaluation of their acidity we analyzed some difference
spectra. Two spectra are shown in Fig. 11, obtained at different
stages of evacuation and at relatively low CO coverages. It is clear
that the intensity of the band at 2176 cm1 correlates with the
intensity of the band at ca. 3290 cm1, but there is no correlation
with the intensity of the band at 3615 cm1. However, a good cor-
relation is observed with the intensity of both bands, at 3615 and
3577 cm1. This observation indicates that the band at 3577 cm1
shifts, upon CO adsorption, to ca. 3290 cm1. Detailed analysis re-
vealed that the shifted counterpart of the 3577 cm1 band appears
at slightly lower frequencies. For instance, the maximum of the
shifted band in spectrum b from Fig. 11 appears at wavenumber
with 4 cm1 lower as compared with spectrum a. Analyzing a
series of difference spectra we deduced that the band at
B
0.1
- 3479
- 3663
a
3290 -
- 3615
b
3600 3300
Absorbance
A 0.05
- 2176 -
- 2169
a
b
2200 2180 2160
-1
Wavenumber, cm
Fig. 11. Changes in the FTIR spectra of the desilicated sample induced by
adsorption of CO. Spectrum a, corresponds to the difference between spectra e
and f from Fig. 4, and spectrum b, to the difference between spectra f and h. The
panel A shows the changes in the carbonyl region. The panel B shows the changes in
the OH region.
3577 cm1 is shifted to around 3280 cm1. Thus, DmOH appears
to be ca. 295 cm1, i.e. the 3575 cm1 OH groups are slightly less
acidic than the hydroxyls absorbing at 3615 cm1. This conclusion
is also supported by the stability of the OH. . .CO species: the most
stable ones are formed with the 3615 cm1 OH groups.
It was already proposed that the band at 3577 cm1 (3575 cm1
at rt) corresponded to zeolite acidic hydroxyls. In principle, bridg-
ing OHs with similar frequencies are located in small cavities and
not accessible to bulky molecules. Thus, a band at 3575 cm1 ob-
served with H-MOR is believed to be due to bridged OH groups
in side pockets [17,34] and interacts with CO [17], but not with
benzene [34]. Some experiments to check whether this situation
is realized with our sample were performed (see below).
Finally we shall discuss the OH. . .CO band at 3572 cm1 (Fig. 10,
spectrum b). This shifted OH mode characterizes species of low
stability, somewhat higher that the stability of the SiOH. . .CO spe-
cies formed with the isolated silanols. Since there was no separate
negative OH band changing in concert with the 3572 cm1 band,
we suppose that the band is due to carbonyl complexes formed
with silanols with enhanced acidity.
In summary, compared to the seed-mesostructured material,
the desilicated sample has a more complex hydroxyl spectrum. A
second type of acidic hydroxyls was well detected and some Al
OH species were evidenced. Lewis acid sites were also found.
3.2.4. Low temperature CO adsorption on the parent zeolite
Adsorption of CO on the parent zeolite leads to the appearance
of bands at 2229, 2176, 2157, 2139 and 2135 cm1 (Fig. 12, spec-
trum a). As with the other samples, the bands due to physically ad-
sorbed CO (2139 and 2135 cm1) and SiOH. . .CO species
(2157 cm1) are less stable. A feature of this sample is the appear-
ance of a shoulder located at 2161 cm1 (Fig. 12, spectra bd). At
low coverages (see the inset in Fig. 12) bands due to Al3+CO com-
plexes are detected at 2229, 2223, 2199 and 2192 cm1.
 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
- 2176
2229
3
22
- 2192
-2
0.05
2199
g 0.2
2220 2190 2160
Absorbance
- 2139
- 2135
- 2157
- 2161
- 2229
k
2250 2200 2150
-1
Wavenumber, cm
Fig. 12. FTIR spectra of CO adsorbed on the parent sample. Equilibrium CO pressure
of 200 Pa at 100 K (a), development of the spectra under dynamic vacuum at 100 K
(bi) and at increasing temperature up to 293 K (jn). All spectra are background
and gas-phase corrected.
With this sample the spectra in the OH region are rather nosy
and detailed analysis is hindered. In any case, the shifts of the
silanol band and the bands due to acidic hydroxyls are well de-
tected (Fig. 13). However, the SiOH. . .CO band at 3660 cm1 is
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
shifted OH band at 3660 cm1 to OH. . .CO species formed with
internal silanols with enhanced acidity.
Another peculiarity of the sample is the lack of AlOH species.
Indeed, it is evident from Fig. 12 that there is no carbonyl band
at 2169 cm1 (typical of AlOH. . .CO species). In addition, even
small amounts of AlOH species (not visible in the noisy back-
ground) should produce after CO adsorption an intense shifted
band around 3475 cm1. It is seen from Fig. 13 that no such a band
was produced. Note that the weak absorbance around this fre-
quency is typical of the background spectrum.
Consider now the Al3+ species. A band at 2229 cm1 was regis-
tered and already assigned to c.u.s. tetrahedral aluminum sites. The
band at 2223 cm1 evidences another kind of similar species. The
bands below 2200 cm1, also due to aluminum carbonyls, were de-
tected with reduced intensity as compared with the other samples.
In summary, the parent zeolite sample is characterized by the
highest concentration of acidic bridging hydroxyls. Some internal
silanols with slightly enhanced acidity were also found. In this case
again, Lewis acid sites were detected.
In general, it may be concluded that H-ZSM-12 zeolite is charac-
terized by two types of acidic bridging hydroxyls, the respective IR
frequencies being at 3611 and 3575 cm1. These two OH groups
are characterized by a high acidity as measured by low-tempera-
ture CO adsorption (DmOH of 325 and ca. 295 cm1, respec-
tively). Desilication leads to a strong (ca. 2/3) decrease in
concentration of the Brnsted acid sites. In addition, small amount
of EFAL species holding AlOH groups is formed. The seed-meso-
structured sample is characterized mainly by one type of Brnsted
acid sites (band at 3611 cm1) in a low concentration (ca. 1/9 of the
concentration of the acid sites in the parent zeolite).
299
- 3660
- 3400
Absorbance
d
- 3291
e
3615 -
g
a
a
2100 3800 3600 3400 3200 3000
Wavenumber, cm
-1
Fig. 13. Changes in the FTIR spectra in the OH region induced by adsorption of CO
on the parent zeolite. Background spectrum registered at 100 K (a), in the presence
of 100 Pa CO at 100 K (b), and development of the spectra under dynamic vacuum at
100 K (cg). Spectra bi corresponds to the spectra ah, respectively, from Fig. 4.
Some spectra are shifted along the Y-axis for clarity.
Lewis acid sites (Al3+) were also detected in all samples. These
c.u.s. sites are heterogeneous and probably connected with
originally tetrahedral aluminum. They are in highest concentration
with the desilicated sample.
3.2.5. Adsorption of 1,2,4-TMB on desilicated sample
In order to check for the access of 1,2,4-TMB to the OH groups,
we have studied the adsorption of this substance on the desilicated
sample (where the spectrum of the hydroxyl groups was of best
quality). Adsorption of 1,2,4-TMB (equilibrium pressure of
100 Pa) leads to strong decrease in intensity of the silanol bands
at 3745 cm1 and appearance of broader band at 3581 cm1
(Fig. 14, spectrum a). These results allow assigning the band at
3581 cm1 to silanols connected to 1,2,4-TMB via H-bond, the in-
duced shift Dm = 164 cm1. In addition, bands due to adsorbed
1,2,4-TMB are seen (for instance the bands in the 3150
2820 cm1 region).
The 3581 cm1 band masks the bands due to bridging OH
groups and does not allow drawing, at this stage, any conclusions
on whether 1,2,4-TMB has affected or not the bands at 3611 and
3575 cm1. Further evacuation at rt and 373 K leads to decrease
in intensity of the band at 3581 cm1 until its full disappearance
(Fig. 14, spectrum b) and the band at 3746 cm1 (SiOH groups)
is, to a big extent, restored. Simultaneously, the bands characteriz-
ing adsorbed 1,2,4-TMB decreases in intensity.
The disappearance of the 3581 cm1 band after evacuation at
373 K reveals some other peculiarities of the spectra. First, it is
now well seen that the bands characterizing bridging hydroxyls
(3511 and 3575 cm1) and Al-OH groups (3660 cm1) are con-
sumed and a broad band at 3247 cm1 appeared at their expense.
Unfortunately, the shifted band, although showing asymmetry, is
not well resolved and we can only make the general conclusion
that the OH modes at 3611 cm1 are red shifted with ca.
365 cm1 upon 1,2,4-TMB adsorption.
Secondly, it becomes clear that a broad feature centered at ca.
3325 cm1 was present in the spectrum recorded under 100 Pa
300 L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301
0.2
3581 -
Absorbance
- 3247
- 3575
- 3611
- 3746
3800 3600 3400 3200
Wavenumber, cm
Fig. 14. Changes in the FTIR spectra in the OH/CH regions induced by adsorption of
1,2,4-TMB at rt on the desilicated sample. Equilibrium 1,2,4-TMB pressure of 100 Pa
(a) (spectrum divided by a factor of two) and after 10 min evacuations at 373 (b),
423 (c) and 473 K (d). Some spectra are shifted along the Y-axis for clarity.
equilibrium pressure of 1,2,4-TMB (Fig. 14, spectrum a) (note that
this spectrum is divided by two for better visualization). These re-
sults can be rationalized assuming existence of a fraction of sila-
nols with enhanced acidity (leading to a higher shift of the OH
modes upon formation of H-bond) and are consistent with the
CO adsorption results.
Evacuation at 423 K leads to a strong decrease in intensity of the
band at 3247 cm1 and those characterizing adsorbed 1,2,4-TMB
while an important fraction of the acidic hydroxyls was recovered
(Fig. 14, spectrum c). Surprisingly, the negative band at 3745 cm1
gained some intensity. This effect was even more pronounced after
evacuation at 473 K, temperature that ensured practical desorption
of all of the preadsorbed 1,2,4-TMB (Fig. 14, spectrum d). There-
fore, we may conclude that adsorption/desorption of 1,2,4-TMB
promotes sample dehydroxylation. A careful inspection of the
spectra indicates some dehydroxylation involving bridging
hydroxyls.
Let us now discuss the location of the bridging hydroxyls. The
band at 3611 cm1 is at a position typical of hydroxyls in 12-mem-
bered ring channels, as those in ZSM-12 [7]. On the other hand, the
frequency of the band at 3575 cm1 is rather characteristic of OH
groups in 8-membered rings where they experience a stronger
electrostatic interaction with zeolite oxygens. However, our results
clearly show that the 3575 cm1 hydroxyls are accessible to 1,2,4-
TMB. Based on this, and taking into account that ZSM-12 has uni-
dimensional 12-membered ring channels, one can conclude that
the OH groups under consideration are also located in the main
channels. Most probably they are in positions that mimic smaller
rings. Further investigations are needed for more exact determina-
tion of the location of these hydroxyls.
3.3. Catalytic test
The catalytic conversion of 1,2,4-TMB includes its isomerization
to 1,2,3-TMB and 1,3,5-TMB, disproportionation to mixture of xy-
lenes and tetramethylbenzene isomers (TeMB), dealkylation of
the reactant and reaction products, as well as coke formation.
The total 1,2,4-TMB conversion as a function of the time on stream
at reaction temperatures 573, 673 and 723 K for the studied sam-
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-
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
to [36] is the loss of strong acid sites, induced by the alkali
b treatment.
It is observed that the degree of 1,2,4-TMB conversion of the
c parent and desilicated samples tends to equalize with the time
on stream. The latter sample is obviously more stable and deacti-
vates slower (Fig. 15A). Very recently, for hierarchically structured
d
micromesoporous ZSM-5 zeolite, remarkably high resistance to
deactivation in the reaction of isomerization of 1,2,4-trimethylben-
zene (although at about two times lower conversions than the ob-
3000 2800 served in the present work) has been found by Ryoo et al. [4]. The
-1 observed, in the present work, slower deactivation of desilicated
sample is in accordance with its higher specic surface area and
pore volume, determined by low temperature N2 adsorption (see
Table 1). At lower temperature (573 K) parent sample and desili-
cated sample, after about 20 min time on stream, show close de-
gree of conversion. Taking into account that the difference in the
adsorption rate of 1,2,4-TMB on the microporous sample 1 and
the desilicated sample 2 is insignicant (Fig. 3 A and B), it can be
concluded that the process of mass-transfer is not rate determining
for the 1,2,4-TMB transformations. Therefore, the acid strength and
density of the accessible acidic sites seems to determine the cata-
lytic transformation of 1,2,4-TMB on the studied zeolite samples.
This assumption is in agreement with the acidity order of studied
samples: microporous ZSM-12 > desilicated ZSM-12 > seed-meso-
structured ZSM-12, found by the FTIR spectroscopy of adsorbed
CO and the 27Al-MAS NMR spectroscopy.
The selectivity toward reactions of isomerization (to 1,2,3-TMB
and 1,3,5-TMB,) and disproportionation (to xylenes and tetrameth-
ylbenzenes) with time on stream upon 1,2,4-TMB conversion at
temperature of 673 K are shown in Fig. 16A and B, respectively.
60
A 60
B 60
C
1,2,4-TMB total conversion, mol.%
50 50 50
40 40 40
30 30 30
20 20 20
10 10 10
Treact.=723 K Treact.=673 K Treact.=573 K
0
0 40 80 120 160 200 0 40 80 120 160 200 0 40 80 120 160 200
Time on stream, min
Fig. 15. Dependence of the 1,2,4-TMB total conversion on the time on stream over
starting H-ZSM-12 zeolite (solid squares), desilicated H-ZSM-12 (open circles) and
seed-mesostructured H-ZSM-12 (solid triangles) at contact time of 0.36 h and
reaction temperatures of 723 K (A), 673 K (B) and 573 K (C).

100
A 100
90
Selectivity to disproportionation, %
Selectivity to isomerization, %
80
70
60
50
40
30
20
10
0 40 80 120
Time on stream, min
Fig. 16. Selectivity to isomerization of 1,2,4-TMB (sum of 1,3,5-TMB and 1,2,3-
TMB), (A), and selectivity to disproportionation (sum of xylenes and TeMBs), (B) at
673 K and contact time 0.36 h in dependence on the time on stream: (parent sample
(solid squares), desilicated sample (open circles) and seed-mesostructured sample
(solid triangles).
Compared to the parent zeolite, the desilicated sample, at close de-
gree of conversion, reveals more intense isomerization at the ex-
pense of the disproportionation.
It is known that the formation of bulky biphenylmethane carbo-
cation intermediates is a necessary step for the disproportionation
reaction of 1,2,4-TMB [37]. For the formation of this intermediate,
two adjacent acid sites on the catalyst surface, with appropriate
acidity, are required. The reaction of disproportionation requires
stronger acid species than the reaction of isomerization. In accor-
dance with the above mentioned, the most acidic parent zeolite,
is less selective toward reaction of 1,2,4-TMB isomerization
(Fig. 16A) but shows highest selectivity among studied samples
to the disproportionation reaction (Fig. 16B).
The desilicated and the seed-mesostructured samples, both
characterized with lower acidity than the parent zeolite, obviously
posses better tuned acidity for the reaction of isomerization (70
75% selectivity to isomerization) after about 120 min time on
stream. The increased selectivity to isomerization during the
course of reaction (Fig. 16A) could be also a result of coke forma-
tion and blockage of the most acidic sites, conducting the reactions
of disproportionation and dealkylation on the catalysts.
4. Conclusions
In the present work microporous H-ZSM-12, desilicated H-ZSM-
12 and seed-mesostructured H-ZSM-12 samples are compared.
As measured by low-temperature CO adsorption, the micropo-
rous H-ZSM-12 zeolite is characterized by two types of highly
acidic bridging hydroxyls, with IR frequencies at 3611 and
3575 cm1. Desilication leads to a strong (ca. 2/3) decrease in con-
centration of the Brnsted acid sites. In addition, small amount of
EFAL species holding OH groups is formed. The seed-mesostruc-
tured sample is characterized mainly by one type of Brnsted acid
sites (band at 3611 cm1) in a low concentration (ca. 1/9 of the
concentration of the acid sites in the parent zeolite). The acidity
of the studied samples is in the following order: microporous H-
ZSM-12 > desilicated H-ZSM-12 > seed-mesostructured H-ZSM-
12. This order is in agreement with the dada from 27Al-MAS NMR
spectra.
L. Dimitrov et al. / Microporous and Mesoporous Materials 143 (2011) 291301 301
B The studied samples show high catalytic conversion and rela-
tively good stability in the reactions of 1,2,4-trimethylbenzene
90
transformations. At the experimental conditions studied, the de-
Treact.=673 K gree of 1,2,4-TMB conversion seems to be governed by the acid
80
strength and the density of the accessible Brnsted acid sites.
70 The acid site density of the desilicated and seed-mesostructured
H-ZSM-12 samples is better tuned for the conduction of selective
60
isomerization of 1,2,4-TMB. The microporous H-ZSM-12 zeolite,
50 due to its higher acidity, could be more adequate for applications
where disproportionation reactions are preferable.
40
30 Acknowledgments
20 This work was supported by the Bulgarian Scientic Fund
(Grants DTK 02/47, DO 02-184 and DCVP 02/2).
10
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