Brazilian Journal

of Chemical ISSN 0104-6632

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Vol. 24, No. 01, pp. 135 - 141, January - March, 2007

SYNTHESIS AND CHARACTERIZATION OF

Al- AND Ti-MCM-41 MATERIALS: APPLICATION
TO OXIDATION OF ANTHRACENE
R. S. Araújo1†, F. S. Costa2, D. A. S. Maia2, H. B. Sant`Ana2 and C. L. Cavalcante Jr.2*
1
Programa de Pós-Graduação em Química Inorgânica, Universidade Federal do Ceará,
Campus do Pici, Bl. 940, Fortaleza, CE - CEP 60455-760, Brazil.
†
Current Address: CEFETCE, Centro Federal de Educação Tecnológica do Ceará,
Av. 13 de Maio 2081, CEP: 60040-531, Fortaleza - CE, Brazil.
2
Grupo de Pesquisas em Separações por Adsorção (GPSA), Departamento de Engenharia Química,
Phone: +(55) (85) 3366-9611, Fax: +(55) (85) 3366-9601, Universidade Federal do Ceará,
Campus do Pici, Bl. 709, CEP: 60455-760, Fortaleza - CE, Brazil,
E-mail: celio@gpsa.ufc.br

(Received: March 28, 2005 ; Accepted: December 20, 2006

Abstract - The synthesis and characterization of new molecular sieves of the MCM-41 type are presented in
this study. Samples were obtained from the alkoxides of Si, Ti and Al and different long-chain amine and
alkylammonium salts surfactants, by the sol-gel method, through moderate agitation at room temperature. The
reactions were conducted in two steps, acid hydrolysis (pH=2) and alkaline condensation (pH=10), both
taking about 90min. The synthesized crystals were characterized using infrared spectroscopy,
thermogravimetry and X-Ray diffraction. Pore diameters and surface areas were measured by N2 adsorption at
77K. Catalytic tests were conducted for anthracene oxidation using different oxidants (H2O2,
alkylhydroperoxide) and organic solvents (benzene, tetrahydrofuran).
Keywords: Synthesis; Characterization; MCM-4; Anthracene oxidation.

INTRODUCTION (Reddy and Song, 1996; Selvam et al., 2000; Corma

et al., 1994). This structural characteristic is a limiting
Porous solids are widely used in industrial factor for the processing of higher molecular weight
applications related to the preparation of adsorbents, hydrocarbons (Biz and Occelli, 1998). In 1992 a
catalysts and ion-exchangers as well as for future use significant change took place in nanoporous science
in advanced technologies involving semiconductors, when Mobil researchers reported an aluminosilicate
photoreceptors, and enzymatic complexes (Sayari, synthesis with uniform size in the mesoporous
1996). Zeotypical structures with pore diameters materials range (2 to 50nm) (Beck et al., 1992; Kresge
ranging from 2 to 12Å have traditionally been used in et al., 1992). These materials, named M41S, have
catalytic processes. These materials are subdivided structural characteristics directly related to the
into three main categories: zeolites (e.g., A, X, Y), conditions of the synthesis: nature of the surfactant,
aluminum phosphates (AIPO´s) and metalophosphates pH, presence of electrolytes, temperature, solvents,
with large pores (VPI-5, JDF-20, etc). Several and time of reaction (Cassiers et al., 2000; Ryoo and
industrial processes use microporous zeolites with Kim, 1995; Arnold et al., 1999).
pore diameters ranging from 0.5 to 0.6nm in the The main difference in the preparation of zeolites
separation and catalysis phases (e.g. catalytic and of M41S-type materials consists in the action of
cracking, xylenes separation and isomerization) directing surfactant agents (templates), which

*To whom correspondence should be addressed

136 R. S. Araújo, F. S. Costa, D. A. S. Maia, H. B. Sant`Ana and C. L. Cavalcante Jr.

organize themselves in water solution forming either Si+Al alkoxides, a water solution of
specific compositions or liquid crystals (Sayari, cetiltrimethylammonium chloride was added. For the
1996). According to this mechanism, the Mobil Ti-MCM-41 samples, either an alcohol solution of
scientists found three different forms: a hexagonal dodecylamine or an acid water solution (pH=1) of
phase, a hexagonal arrays of molecules (MCM-41 dodecylamine (salt preparation in situ) was added.
family); a cubic phase (MCM-48 family); and an The molar composition of the synthesis gel was 1
unstable lamellar phase (MCM-50 family). Various TEOS : 0.033 alkoxide (Ti or Al): 0.30 Surfactant:
synthesis strategies are used in the preparation of the 5.2 Ethanol: 23 H2O. The reaction was initially
mesostructured materials, especially the following: conducted at pH 2.0 (alkoxide hydrolysis) for about
the hydrothermal method (typically described as the 90min under moderate agitation. At the end of the
treatment of a silicate solution between 80 and 140ºC operation, the pH of the solution was adjusted to 10
for two or more days) and the sol-gel method with 30% ammonium hydroxide. The time of agitation
(related to the hydrolysis and condensation of varied between 75 and 90 min. Once the alkaline phase
metallic alkoxides at specific pHs). had ended, the material was left still for 20h at room
There has recently been an increased interest in temperature. Later the following phases were carried
the insertion of metals with high redox potentials (V, out: filtration in vacuum, washing with deionized
Cr, Ti, Fe, Ni, etc) into the original structure of the water, drying (6h at 105ºC), and calcination (550-
MCM-41 type (Ulagappan and Rao, 1996; 600ºC in air atmosphere). The synthesized samples
Rodriguez-Castellón et al., 2003; Tuel, 1999; Blasco were named Al-CTACl, Ti-DA, and Ti-DACl.
et al., 1995). These metals produce isomorphic
substitutions that increase the catalytic activity in b) Characterization
oxidative processes involving organic molecules of
commercial interest, such as phenols, bulky The samples were characterized by four
aromatics, and terpineols (Kondam and Song, 1996). analytical techniques as follows: X-Ray diffraction
This study will present results of synthesis and (DRX) in a Philips X’PertPro diffractometer using
characterization of Aluminum and Titanium MCM-41 CuKα radiation (40KV and 40mA); infrared
materials prepared in our laboratory using different spectroscopy (FTIR) in a Bio-Rad spectrophotometer,
surfactants and evaluated for the reaction of anthracene using the attenuated total reflection technique
oxidation using different oxidants and solvents. (ATR); thermogravimetric analysis (TG/DTG) in a
Shimadzu 5OH system with a platinum crucible, a
synthetic air atmosphere, a 50cc/min flow; and
EXPERIMENTAL SECTION specific surface area (ABET) in a QuantaChrome
Nova 2000 system. The same equipment was used to
Materials calculate the pore distribution by the BJH method.
All the reactants (alkoxides, solvents, oxidants, c) Catalytic Tests and Product Analysis
amine, alkylammonium salt, hydrocloric acid,
ammonium hydroxide, anthracene and 9,10- Anthracene oxidation was used as a model
anthraquinone), of analysis grade (> 98%), were reaction (see Figure 1) to assess the catalytic activity
supplied by ACROS ORGANICS with analytic purity of the synthesized mesoporous materials. Batch
degree (and used without any further purification. catalytic tests were carried out in a bottom flask
under magnetic agitation with anthracene dissolved in a
Methods solvent (either benzene–C6H6 or tetrahydrofuran–THF),
followed by addition of the catalyst and the oxidant
a) Synthesis (either H2O2 30% or tert-butyl hydroperoxide–TBHP
70%). The reaction mixture was then left under
The MCM-41 metal samples were prepared by the reflux, while the change in the typical brown color of
sol-gel method with the use of the alkoxides tetraethyl the quinones was observed. The reaction conditions
orthosilicate-TEOS (silicon), aluminum triisopropoxide used were as follows: catalyst/anthracene mass ratio
(aluminum), and titanium tetraisopropoxide (titanium), of 1:1; solvent volume of 10mL; molar ratio
and the surfactant agents dodecylamine (DA), anthracene/oxidant of 1:10; and time of reaction of
dodecylamine hydrocloride (DAC1), and 20h (Srinivas et al., 2002). The reaction was followed
cetiltrimethyammonium chloride (CTACl). The typical by high performance liquid chromatography using a
procedure involves addition of alkoxides of Ti or Al Varian ProStar 150 model with a isocratic mode of
to the TEOS in a Teflon flask, followed by dilution 1mL/min flow of a mixture CH3CN-H2O 80:20, λ =
of the mixture with ethanol. For the initial mixture of 254nm.
Brazilian Journal of Chemical Engineering
 Synthesis and Characterization of Al- and Ti-MCM-41 Materials 137

catalyst
solvent, oxidant

Figure 1: Model reaction used in the catalytic tests (anthracene Æ 9,10-anthraquinone)

RESULTS AND DISCUSSION samples were prepared using Si/metal molar ratios of
approximately 30:1 in the synthesis gel.
Synthesis of Mesoporous Materials in Different
Surfactant Media Characterisation by XRD, BET, TG/DTG, FTIR

The main characteristic of catalyst preparation by a) X-Ray Diffraction

the sol-gel method is the presence of an acid phase
that keeps the Al+3 and Ti+4 ions in solution. For the The diffraction profiles of the three synthesized
titanium catalysts this is a compulsory phase, since samples are presented in Figure 2. It is possible to
carrying out the process (hydrolysis and observe a peak for 2θ between 2º and 3º, which is
condensation) in a purely alkaline medium would characteristic of the Bragg plane reflection (100).
produce the direct precipitation of titanium oxide, or
This is sufficient evidence of the presence of the
TiO2, from the alkoxide (Luo et al., 2002). The types
of gel initially elaborated were viscous suspensions MCM-41 structure (Blasco et al., 1995). There are
that were easy to filtrate. After removal of the no (110), (200), and (210) Bragg planes, which
surfactants through calcination at 600ºC, an demonstrates poor ordering of the pore structure of
extremely thin white powder was obtained. All our synthesized samples.
Intensity (a.u.)

Ti-DA

Al-CTACl

Ti-DACl

1 2 3 4 5 6 7 8 9 10

2Θ (degree)

Figure 2: X-Ray profiles of the calcined samples.

b) N2 Adsorption the synthesized materials, despite lower than usual

values observed for the surface areas that were
Surface areas (ABET) were determined from N2 measured. This can be related to the lower
adsorption at 77K in a BET plot linear band (P/P0 crystallinity that was observed in the X-ray
= 0.05-0.30). The isotherms obtained were of type diffraction analysis indicative of the poor ordering
IV, in accordance with the IUPAC classification of the pore structure of our samples. The pore
for mesoporous materials (Sing, 1998). The diameters (between 2.8 and 3.2 nm) are in the
physical properties of the synthesized samples are range usually observed for MCM-41 samples
listed in Table 1. The values for surface areas and (Corma et al., 1994; Chen et al., 1999; Aguado et
pore diameters confirm the mesoporous nature of al., 2000).

Brazilian Journal of Chemical Engineering Vol. 24, No. 01, pp. 135 - 141, January - March, 2007
138 R. S. Araújo, F. S. Costa, D. A. S. Maia, H. B. Sant`Ana and C. L. Cavalcante Jr.

Table 1: Properties of calcined Al-MCM-41 and Ti-MCM-41 samples.

Samples
Properties
Ti-DA Ti-DACl Al-CTACl
d100 (Å) 37.5 36.2 33.1
a0* (Å) 43.3 41.8 38.3
ABET (m2/g) 726 657 595
Pore diameter (Å) 28.1 31.1 32.0
* a0 = 2d100 / 31/2 (unit hexagonal cell parameter)

c) Thermal Analysis (TG/DTG) corresponding to the removal of the surfactant. It

may also be observed that moderate losses are
The thermogravimetric curves (TG) and the noted between 550 and 600oC, which may be
respective differential curves (DTG) are shown in attributed to dehydration and condensation of
Figure 3. In all samples, thermal degradation silanol groups at the surface of the samples
peaks are observed, between 150 and 370ºC, (Cesteros et al., 2001).

11.0

10.5
DTG
10.0

9.5

9.0
Weight (%)

8.5 TG
8.0

7.5

7.0

6.5
Ti-DA
6.0

10.5

10.0

9.5 DTG

9.0
Weight (%)

8.5

8.0

7.5
TG
7.0

6.5
Al-CTACl
6.0

10.5

10.0
DTG
9.5

9.0
Weight (%)

8.5
TG
8.0

7.5

7.0

6.5
Ti-DACl
6.0
50 100 150 200 250 300 350 400 450 500 550 600 650
o
Temperature ( C)

Figure 3: TG/DTG analyses of the dry samples.

Brazilian Journal of Chemical Engineering
 Synthesis and Characterization of Al- and Ti-MCM-41 Materials 139

d) IR Spectroscopy (FTIR) cm-1 which is associated to asymmetrical tensions of

Si-O-Si in the framework structures. Finally, the
The infrared spectra of the synthesized samples presence of a weak band situated between 960 and
are shown in Figure 4. Special attention should be 970 cm-1, which is associated with the Si-O-R
paid to a few points. First, the presence of an stretching, where R = H+, Ti+4, or Al+3. The
intense band between 4000 and 3000 cm-1 in all intensity of this band may be related to the amount
samples which corresponds to the internal and of metals (Ti or Al) incorporated to the framework
external hydroxyl groups of the mesoporous structure (Zholobenko et al., 1997; Chen et al.,
structure. Second, a band between 1050 and 1250 1997).

Ti-DA
% transmittance

Al-CTACl

Ti-DACl

4000 3600 3200 2800 2400 2000 1600 1200 800 400
-1
Wavenumber (cm )

Figure 4: Infrared spectra of the Ti-DA sample after calcination

Catalytic Results and was thus selected for the studies of oxidant and
solvent effects that followed. For comparison,
We performed comparative oxidation reaction tests Srinivas et al. (2002) using a Ti-MCM-41 sample in a
using the samples we synthesized at the same reaction system with TBHP and benzene observed conversion
conditions as reported by Srinivas et al. (2002). We and selectivity of 6.7% and 33.1%, respectively.
also carried out the reaction at the same conditions in To evaluate the effect of solvent and oxidant type
the absence of a catalyst (with insignificant on the anthracene oxidation reaction, we performed
conversion to 9,10-anthraquinone), and using a similar tests using benzene (C6H6) and
commercial Y microporous zeolite (Si/Al=1.6), to tetrahydrofurane (THF) as solvents, and hydrogen
compare with our samples. All results of conversion peroxide (H2O2) and tert-butyl hydroperoxide (TBHP)
and selectivity are listed in Table 2. It may be as oxidants. Table 3 shows all the conversion and
observed that all mesoporous samples have better selectivity results. The best combination was for
selectivity and conversion than the Y microporous benzene as solvent and TBHP as oxidant, which
zeolite for this reaction. It may also be noted that the yielded the best combined results of conversion and
sample entitled Ti-DA (titanium MCM-41 prepared selectivity. It may be noted that for the benzene-H2O2
using dodecylamine as surfactant) yielded the higher system, where the polarities of the species are too
values for conversion and selectivity (71.2% and different, the conversion and selectivity to 9,10-
98.8%, respectively) of the three mesoporous samples, anthraquinone proved to be insignificant.

Table 2: Effect of the type of catalyst on anthracene oxidation. Conditions: benzene 10mL,
anthracene/TBHP 1:10 (molar), 0.1g catalyst, 0.1g anthracene, reaction time 20h.

Catalyst Conversion (%) Selectivity (%)

Al-CTACl 55.7 78.1
Ti-DACl 48.2 97.2
Ti-DA 71.2 98.8
Y 23.1 52.1
no catalyst 0.62 0.82

Brazilian Journal of Chemical Engineering Vol. 24, No. 01, pp. 135 - 141, January - March, 2007
140 R. S. Araújo, F. S. Costa, D. A. S. Maia, H. B. Sant`Ana and C. L. Cavalcante Jr.

Table 3: Effect of solvent and oxidant type on anthracene oxidation. Conditions: solvent 10mL,
anthracene/oxidant 1:5 (molar), 0.1g Ti-DA, 0.1g anthracene, reaction time 20h.

Solvent/Oxidant Conversion (%) Selectivity (%)

C6H6 /H2O2 8.2 3.3
THF /H2O2 72.1 44.3
C6H6/TBHP 71.2 98.8
THF /TBHP 70.8 50.2

CONCLUSIONS Arnold, A. B. J., Niederer, P. M., Nießen, T. E. W.

and Hölderich, W., The influence of synthesis
Al-MCM-41 and Ti-MCM-41 samples were parameters on the vanadium content and pore size
synthesized using the sol-gel method and different of V-MCM-41 materials. Microporous and
surfactants. The samples were characterized by Mesoporous Materials, 28, 353, 1999.
infrared spectroscopy, N2 adsorption, X-ray Beck, J.S., Vartuli, J.C., Roth, W.J., Leonowicz,
diffraction, and thermal analysis. The samples were M.E., Kresge, C.T., Schmitt, K.D., Chu, C.T.-W.,
also tested for a previously reported oxidation Olson, D.H., Sheppard, E.W., McCullen, S.B.,
reaction of anthracene to 9,10-anthraquinone Higgins, J.B. and Schlenker, J.L., A new family
(Srinivas et al., 2002) and evaluated with regards to of mesoporous molecular sieves prepared with
solvent and oxidant effect. Our results indicate much liquid crystal templates. J. Am. Chem. Soc., 114,
better conversions and selectivities for our 10834, 1992.
mesoporous samples as compared to a microporous Biz, S. and Occelli, M.L., Synthesis and
zeolite, which may be further studied to try to more Characterization of Mesostructured Materials,
deeply understand the effect of the metal exchange in Catal. Rev. Sci. Eng, Vol 40 (3), p.329-407,
the framework structure. 1998.
Blasco, T., Corma, A, Navarro, M.T. and Pariente,
J.P., Synthesis, Characterization, and Catalytic
ACKNOWLEDGEMENTS Activity of Ti-MCM-41 Structures, Journal of
Catalysis, Vol 156, p.65-74, 1995.
The authors would like to acknowledge the Blasco, T., Corma, A., Navarro, M.T. and Pérez-
financial support received from CNPq, FINEP, and Pariente, J., Synthesis, characterization, and
FUNCAP. Determination of nitrogen adsorption catalytic activity of Ti-MCM-41 structures. J.
isotherms at the laboratory of Prof. Dulce Melo Catal., 156, 65, 1995.
(UFRN) is gratefully acknowledged. XRD analysis Cassiers, K., Van der Voort, P. and Vansant, E.F.,
were kindly performed at the Department of Physics Synthesis of stable and directly usable hexagonal
(UFC). mesoporous silica by efficient amine extraction in
acidified water. Chem. Commun., 2489, 2000.
Cesteros, Y. and Haller, G. L., Several factors
NOMENCLATURE affecting Al-MCM-41 synthesis. Microporous
and Mesoporous Materials, 43, 171, 2001.
ao unit hexagonal parameter Å Chen, L. Y., Ping, Z., Chuah, G. K., Jaenicke, S. and
d100 interplanar distance Å Simon, G., A comparison of post-synthesis
P equilibrium pressure kPa alumination and sol-gel synthesis of MCM-41
P/Po equilibrium relative pressure (-) with high framework aluminum content.
ABET specific surface área m2/g Microporous and Mesoporous Materials, 27, 231,
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Brazilian Journal of Chemical Engineering Vol. 24, No. 01, pp. 135 - 141, January - March, 2007