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J Therm Anal Calorim (2014) 115:3136

DOI 10.1007/s10973-013-3267-0

Kinetic study of template removal of Al-MCM-41 synthesized


at room temperature
Cristiane P. de Macedo Charles A. B. Negrao
Luiz G. M. de Macedo Jose R. Zamian
Geraldo N. da Rocha Filho Carlos E. F. da Costa

Received: 21 January 2013 / Accepted: 21 May 2013 / Published online: 29 June 2013
Akademiai Kiado, Budapest, Hungary 2013

Abstract The Al-MCM-41 molecular sieve with Si/ these materials as catalysts [1]. These mesoporous MCM-
Al = 20 molar ratio was synthesized at room temperature 41 can be synthesized by several routes through the mod-
and characterized by X-ray diffractometry, surface area, ification of variables such as, pH, surfactant concentration,
thermogravimetry, and infrared spectroscopy. The kinetic temperature, silicon source, synthesis time and aging,
study was conducted by Vyazovkin and Ozawa method, in among others. The presence of silanols groups in MCM-41
order to verify the activation energy during the Hofmann allows surface modification of this material. The modifi-
degradation between 130 and 370 C, in which most of cation can be achieved by different ways, such as by direct
surfactant removal occurs. The results suggest that the synthesis or by post-synthesis, but they have the drawback
activation energy for template removal is close to of reducing the pore structure quality when compared to
80 kJ mol-1 lower in Al-MCM-41 synthesized at room pure silicon.
temperature, when compared to results obtained for mes- Direct synthesis can be done by the hydrothermal
opores Al-MCM-41 and MCM-41 synthesized by hydro- method or at room temperature [2]. The hydrothermal
thermal method. This lower activation energy may be method involves heating the reactant at elevated tempera-
understood as consequence of textural properties, such as tures, and needs more synthesis time and more energy
higher pore size. consumption. On the other hand, the advantages of using
the room temperature route range from speed and lower
Keywords Al-MCM-41  Activation energy  Model free cost to the excellent reproducibility [3].
kinetics  Room temperature synthesis A way to improve the performance of MCM-41 as a
catalyst is substituting the Si4? by Al3? in the mesopore
walls [4]. With this substitution, the structure begins to have
Introduction a negative charge that can be compensated by protons, thus
generating the acid Brnsted sites. The number of formed
Researchers seek to enhance the performance of the mes- acid sites depends on the quantity of aluminum inserted
oporous MCM-41 since pure siliceous materials have through synthesis [5]. The resulting solid is commonly used
electrically neutral frameworks, which limit the use of in acid reactions [4], and is known as Al-MCM-41.
Several aluminum sources have been used in room
temperature synthesis of Al-MCM-41, such as aluminum
C. P. de Macedo  C. A. B. Negrao  J. R. Zamian  isopropoxide, aluminum sulfate, aluminum nitrate, alumi-
G. N. da Rocha Filho  C. E. F. da Costa
nate sodium [2], and aluminum chlorite [5]. These
Laboratorio de Catalise e Oleoqumica, Faculdade de Qumica,
Instituto de Ciencias Naturais, Universidade Federal do Para, Al-MCM-41 molecular sieves are attractive due to the
Belem, PA 66075-110, Brazil adjustable pore size, elevated surface area, and because
they have moderate acidity. Besides these advantages, the
L. G. M. de Macedo (&)
calcination procedure can dealuminate the Al-MCM-41,
Faculdade de Biotecnologia, Instituto de Ciencias Biologicas,
Universidade Federal do Para, Belem, PA 66075-110, Brazil hence resulting in mesoporous with small amount of
e-mail: lgm@ufpa.br; drlgmm@gmail.com Brnsted and Lewis acid sites [6].

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32 C. P. de Macedo et al.

The calcination step has attracted the attention of 11NH3:58EtOH:114H2O:0.00112Al, was stirred for 2 h
researchers because it is one of the crucial steps in order to Then the material was aged at room temperature for 20 h,
obtain a material of optimal quality. It is also in this step filtered by vacuum, washed several times with distilled
that the surfactant removal occurs. In general, kinetic study water, and dried at 60 C for 12 h. The obtained solid was
of the surfactant removal is important because the exces- named Al-MCM-41(S).
sive exposure of the material to elevated temperatures can Removal of organic surfactant from Al-MCM-41 sample
destroy its mesoporous characteristics [7]. was performed by calcination: the sample was heated from
On the other hand, when kinetics of complex reactions is room temperature to 540 C at a heating rate of 5 C min-1,
studied, such as the decomposition of the surfactant or the and under nitrogen atmosphere (100 mL min-1). After
thermal decomposition of fuel oils, the traditional kinetic reaching the 540 C temperature, nitrogen flow was replaced
methods cannot be normally applied. For this reason, by synthetic air, at a rate flow of 100 mL min-1. The iso-
methods have been developed in order to investigate the thermal treatment was kept at the same temperature for 2 h.
kinetics of these reactions [8]. For example, some studies This sample was labeled as Al-MCM-41(C).
report the kinetic data of the surfactant removal from
molecular sieves MCM-41 and Al-MCM-41 synthesized
Sample characterization
by the hydrothermal method with different silica sources
[7, 9, 10], using the methods developed by Ozawa [11] and
X-ray diffraction (XRD)
Vyazovkin [12, 13].
This study focuses the kinetic study of the removal of
X-ray diffractions were obtained on a PANalytical,
the organic template cetyltrimethylammonium bromide
XPERT PRO MPD (PW 3040/60) diffractometer, using
(CTAB) by Ozawa and Vyazovkin methods from Al-
powder method, at a 1.5 \ 2h \ 6 interval. Co Ka
MCM-41 synthesized at room temperature, as well its
(40 kV and 40 mA) radiation was used. The 2h scanning
characterization. The literature data on such template
speed was 0.02 min-1.
removal for Al-MCM-41 and MCM-41 obtained under
hydrothermic synthesis conditions are also compared with
the present results. N2 adsorptiondesorption

Nitrogen adsorptiondesorption isotherms were obtained at


Experimental liquid nitrogen temperature using a Micromeritics TriStar
II model 3020 V1.03 apparatus. Before each measurement,
Materials the sample was outgassed at 300 C for 2 h. The specific
surface area was determined according to the standard
The reactants used were: cetyltrimethylammonium bro- BrunauerEmmettTeller (BET) [15]. Pore diameter and
mide (CTAB, Aldrich), absolute ethylic alcohol (Nuclear), pore volume obtained by the BarrettJoynerHalenda
ammonium hydroxide (Cromoline), hydrated aluminum (BJH) method [16] .
nitrate (Vetec), and Tetraethoxysilane (TEOS, Aldrich).
The reactants were used without previous treatment. Thermal analysis (TG/DTA)

Al-MCM-41 synthesis The thermal decomposition of Al-MCM-41(S) sample was


carried out on a simultaneous TG/DTA (Shimadzu DTG-
The material was synthesized according to the procedure 60H) thermogravimetric analyser. About 5 mg of the
described in the literature [14] with hydrated aluminum samples were placed in platinum pans and heated from
nitrate as source of aluminum. 2.5 g of CTAB was dis- room temperature to 700 C, at heating rates of 5, 10, 15,
solved in deionized water under vigorous stirring. 60 g of 20, and 25 C min-1 in a nitrogen flux of 50 mL min-1. To
absolute ethanol was added to this mixture, with later obtain activation energy, the Ozawa [11] and Vyazovkin
addition of 16.9 g of a solution of ammonium hydroxide [12, 13] methods were used.
(29 % m/m) under agitation for 15 min. 0.42 g of the
aluminum source was added to the solution, which seemed Fourier transformed infrared spectroscopy (FTIR)
transparent, and afterwards 4.7 g of TEOS was added
drop by drop. The resulting gel obtained after the addition Infrared spectra were recorded in the 4000400 cm-1
of TEOS, with molar composition of 1TEOS:0.3CTAB: spectral region by means of Thermo IR 100 spectrometer.

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Kinetic study of template removal of Al-MCM-41 33

Results and discussion Table 1 Textural properties of the sample Al-MCM-41(C)


da100/ aa0/A SBET/ Pore Pore Network
The information of the Al-MCM-41(S) and Al-MCM- A m2 g-1 diameterb/ volumeb/ contraction/%
41(C) diffractograms were obtained by an X-ray diffraction A cm3 g-1
technique. Figure 1 shows three peaks with reflection of
36.70 42.37 1372 32.39 1.43 9.58
2h = 2.29, 3.92, and 4.54 for the Al-MCM-41(S) sample
a
and 2.39, 4.16, and 4.77 for the Al-MCM-41(C) sample. dhkl and a0were obtained from the XRD data using the formula
a0 = 2d100/31/2
The peak with highest intensity is due to the reflection line b
Pore diameter and pore volume were determined using BJH method
of plane (100), and another two of lower intensity, due to
the reflections of planes (110) and (200), and they are
characteristic of hexagonal mesopores [17]. asymmetric stretch of SiO; (c) in the region
An increase of the intensity of the three peaks was 10891069 cm-1 is related to the asymmetric internal
observed after the calcination process, as well a better stretch of TOT (T = Si, Al); (d) in the region
definition of the higher angle peaks, thus confirming the 974961 cm-1 is related to asymmetric stretch of CH3
hexagonal structure and orderly arrangement [18]. N?; (e) in the region 801795 cm-1 is related to the
The displacement of the peak with highest intensity symmetric stretch of TO (T = Si, Al) [7, 10].
from 2h = 2.29 to 2.39 was observed after calcination, After the calcination process, the vanishing of the bands
suggesting the contraction of the unit cell due to surfac- in 2914 and 2850 cm-1 shown in Fig. 2b indicates that the
tant removal and the condensation of the silanol groups process of surfactant removal was effective and as a result,
(SiOH) [19]. Table 1 shows the results of the textural pore cavities were generated.
properties as pore diameter, pore volume, surface area, net- The thermogravimetric curves for the Al-MCM-
work contraction as well unite cell parameters d100 and a0. 41(S) sample, represented in Fig. 3 indicate three mass
The infrared absorption spectra of the Al-MCM- losses were observed between 30 and 700 C. The first loss
41(S) and Al-MCM-41(C) are shown in Fig. 2. The wide (4.02 %) occurs between temperatures 30 and 130 C, and
band around 34313399 cm-1 is related to hydroxyl it is related to the elimination of physically adsorbed water
groups in the mesoporous structure; the absorption bands or to the evaporation of residual ammonium [20]. The
shown in Fig. 2a in 2914 and 2850 cm-1 are related to the second loss occurs between 130 and 370 C, and it is
stretching of the CH bonds from the CH2 and CH3 groups usually due to the elimination of trimethylamine (N(CH3)3)
of the surfactant species, while the band in through Hofmann degradation. Also, in this step a large
16421644 cm-1 can be assigned to physically adsorbed part of the surfactant (35.92 %) is removed by alkene
water molecules. evaporation (C16H32), and by the fragmentation of the short
Other vibration bands that can be observed are: (a) at carbonic chains, producing CO2, NO2, and H2O. The third
1478 cm-1 is related to the deformation of the CH2 bond; mass loss (5.16 %) was observed in the TG curve between
(b) in the region of 12351217 cm-1 is related to the temperatures 370 and 700 C, and it is usually assigned to

(100)

(110) (a)
Intensity/a.u.

(200)
Transmittance/a.u.

1478

(b)
Intensity/a.u.

1624-1644

(a)
801-795
2850

974-961
2914

3.5 4.0 4.5 5.0


2 /
3431-3399

(b)
1089-1069

(110) (200)
1235-1217

(a)
1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 4000 3500 3000 2500 2000 1500 1000 500
2 / Wavenumber/cm1

Fig. 1 X-ray diffractogram patterns of a Al-MCM-41(S), b Al- Fig. 2 Infrared absorption spectroscopy for material: a Al-MCM-
MCM-41(C) 41(S) and b Al-MCM-41(C)

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34 C. P. de Macedo et al.

0.0005
ZT    
100 Ea R 2 Ea
0.0000 exp  dT  T exp  4
RT E RT
0.0005
0

DTG/% C1
80 0.0010 Substituting the temperature integral and making some
mathematical manipulation gives the following equation
Mass/%

0.0015
used in the Vyazovkin method,
0.0020  
60 b Rk0 Ea
ln 2 ln  5
0.0025 T Ea ga RT
0.0030
40
On the other hand, Eq. 3 could also be treated [27] as
0 100 200 300 400 500 600 700
AEa
Temperature/C g a qx 6
bR
Fig. 3 TG and DTG curves for Al-MCM-41(S) with ratio
10 C min-1 where x = (Ea/RT) and log q(x) % -2.315 - 0.4567x.
From Eq. 6 one can obtain the following expression used in
Ozawa method
the elimination of residual carbonic species and the con-
AEa Ea
densation of silanol groups [2123]. logga log  log b  2:315  0:457 7
The kinetic data of the surfactant removal from the R RT
pores were obtained through thermogravimetric analysis Thus, the activation energy can be obtained from Eq. 7 as
(TG). By applying an isoconversion method on the TG the slope of a plot of logb versus 1/T for fixed values of a
curves, one can obtain the activation energy as a function from experiments at different heating rates b. From Eq. 5,
of conversion a. They are based on the fact that constant similar results can be obtained from a plot of lnb/T versus
conversion of the reaction rate is only a function of tem- 1/T, but now the slope should have the value of -Ea/R.
perature. Furthermore, they are commonly used to obtain In a typical experiment, it is necessary to obtain at least
reliable kinetic information, and also of great advantage three different heating rates b. For the Al-MCM-41(S) TG
since avoid the use of explicit kinetic models [24]. In order curves in this study, five heating ratios were used (b = 5,
to compare directly the results from this study with the 10, 15, 20, and 25 C min-1), with temperature range from
results from literature, Vyazovkin and Ozawa (also known 130 to 370 C regarding to the thermal decomposition of
[25] as Flynn, Wall, and Ozawa or ASTM E698) methods the CTAB by Hofmann degradation [23]. Figure 4 shows
were applied to obtain the value for activation energy. the five conversion curves as a function of the temperature,
In both methods, the dependence of a as a function of time obtained by Eq. 8:
can be expressed as the following differential equation [26],  
mh  mt
a 8
d mh  mf
dT kT  f a 1
a where mh is the initial samples mass, mt is the samples
where k(T) is the temperature dependent rate constant and mass that varies in function of time or temperature, mf is
f(a) is a function that represents the reaction model. The the samples mass in the end of the step to be studied, and a
k(T) is usually represented by the Arrhenius equation, is the conversion.
  The levels of conversion of 10, 20, 30, 40, 50, 60, 70,
da A Ea 80, and 90 % were chosen in order to calculate the acti-
exp  f a 2
dT b kT vation energy by both isoconversion methods. In the
Vyazovkin method for each a conversion the values of lnb/
where A is the pre-exponential factor, b is a constant
T2a were plotted as a function of 1/Ta (represented in
heating rate, R is the gas constant (in J K-1 mol-1), and Ea
Fig. 5a), providing a series of lines with slope -Ea/R. In
is the activation energy. Integrating Eq. 2 gives
the Ozawa method, the logarithm of the heating rate (log b)
ZT   versus the inverse of the absolute temperature (1/Ta) was
A Ea plotted for the three heating rates. Thus, five straight lines
g a exp  dT 3
b RT were obtained (represented in Fig. 5b) with slope -Ea/R,
0
with R = 8,314 J mol-1 K-1.
Now Eq. 3 can be modified in order to be practical. Since The results obtained for the activation energies from the
E/2RT  1, the temperature integral can be approximated by Vyazovkin and Ozawa methods are presented in Table 2.

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Kinetic study of template removal of Al-MCM-41 35

Table 2 Activation energy for the conversion of 1090 % of Al-


100 5 C min1
MCM-41(S) obtained by Vyazovkin and Ozawa models
10 C min1
15 C min1 Conversion/% Vyazovkin Ea/kJ mol-1 Ozawa Ea/kJ mol-1
80
20 C min1
25 C min1 10 85.16 85.08
Conversion/%

60 20 82.97 79.60
30 83.45 79.97
40 40 87.28 83.62
50 85.08 81.34
20 60 86.55 82.64
70 91.83 87.84
0 80 93.54 89.47
150 200 250 300 350 400 90 100.94 96.80
Temperature/C Ea average 88.53 5.87 85.15 5.50

Fig. 4 Conversion curve as a function of the temperature of Al-


MCM-41(S)
removal from MCM-41 through the Ozawa method, obtaining
At 10 % conversion, Vyazovkin and Ozawa methods a value of 173.7 23 kJ mol-1. With the insertion of alu-
suggests an activation energy of 85.16 and 85.08 kJ mol-1, minum in the structure (Al-MCM-41), Araujo et al. [10]
respectively. As the conversion goes on, the activation reports values obtained by the Vyazovkin method, of 165.8
energy slightly increases and at 90 % conversion, the and 270.1 kJ mol-1 for the temperature ranges of 100310 C
activation energies obtained by Vyazovkin and Ozawa and 310600 C. One possible explanation for the difference
methods are 100.94 and 96.80 kJ mol-1, respectively. of the activation energy values obtained in this study, and the
Since Ea varies with a, this point should be interpreted in values obtained by Souza [9], Araujo [10] and Braga [7] can
terms of multi-step mechanisms [25]. be understood as a function of the pore size: For example,
The mean activation energy values for surfactant removal textural properties regarding pore size obtained by room
obtained in the range of 1090 % of conversion suggested by temperature synthesis in this study like SBET and pore vol-
the Vyazovkin and Ozawa methods were, respectively, ume (1372 m2 g-1 and 1.43 cm3 g-1) are larger than ones
88.53 5.87 and 85.15 5.50 kJ mol-1. These results are obtained by Braga (757 m2 g-1 and 0.63 cm3 g-1). Higher
close to 80 kJ mol-1, lower than the ones reported in the pore size would give less diffusional resistance and would be
literature for mesoporous obtained through hydrothermal more effective toward template removal. Although Souza [9]
synthesis: Souza et al. [9] reports the value of 166 and Araujo [10] didnt publish the textural parameters, it is
8.2 kJ mol-1, and Braga et al. [7] reports the value of sensible to expect that Souzas values should be similar to the
177.26 26 kJ mol-1, both being results for mesopores ones from Braga, based on the fact that ticker pore wall
MCM-41 without the addition of aluminum, and using the samples are formed in higher temperatures [28], resulting in
Vyazovkin method. Braga et al. [7] also studied the surfactant lower surface areas and pore volume values.

Fig. 5 Linear fits of the a 1.2 b 1.7


logarithms of heating rate
1.1 1.6
versus the reciprocal absolute 90 %
temperature for different 1.0 1.5 10 %
60 % 90 % 60 % 30 %
extends of conversion: a using 0.9 30 % 10 % 1.4
Vyazovkin model and b using 0.8
Log /C cm1
Ln /T 2/T 2

the Ozawa model 1.3


0.7
1.2
0.6
0.5 1.1
0.4 1.0
0.3 0.9
0.2 0.8
0.1
0.7
0.0
0.6
1.7 1.8 1.9 2.0 2.1 2.2 1.7 1.8 1.9 2.0 2.1 2.2
1000/T/K1 1000/T/K1

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36 C. P. de Macedo et al.

Conclusions 10. Araujo AS, Fernandes VJ, Souza MJB, Silva AOS, Aquino
JMFB. Model free-kinetics applied to CTMA? removal Al-
MCM-41 molecular sieves. Thermochim Acta. 2004;413:23540.
A mesoporous molecular sieve Al-MCM-41 was synthe- 11. Ozawa T. A new method of analyzing thermogravimetric data.
sized at room temperature and initially characterized by Bull Chem Soc Jpn. 1965;38:18816.
X-rays diffraction confirming the hexagonal ordering of the 12. Vyazovkin S, Goryachko V. Potentialities of software for kinetic
structure. The kinetic studies done in this study through the processing of the thermoanalytical data by the isoconversion
method. Thermochim Acta. 1992;194:22130.
Ozawa and Vyazovkin methods suggest that the Al-MCM- 13. Vyazovkin S, Wight CA. Model-free and model-fitting approa-
41 synthesized at room temperature is close to 80 kJ mol-1 ches to kinetic analysis of isothermal and nonisothermal data.
lower activation energy for template removal than the Thermochim Acta. 1999;340341:5368.
Al-MCM-41 obtained by hydrothermal synthesis. In other 14. Szegedi A, Konya Z, Mehn D, Solymar E, Pal-Borbely G, Hor-
vath ZE, Biro LP, Kiricsi I. Spherical mesoporous MCM-41
words, the activation energy for template removal value for materials containing transition metals: synthesis and character-
room temperature synthesized Al-MCM-41 is practically ization. Appl Catal A Gen. 2004;272:25766.
half of the correspondent activation energy value obtained 15. Brunauer S, Emmett PH, Teller E. Adsorption of gases in mul-
from hydrothermal synthesis, and this probably occurs due timolecular layers. J Am Chem Soc. 1938;60:30919.
16. Barrett EP, Joyner LG, Halenda PP. The determination of pore
to textural and pore characteristics. volume and area distributions in porous substances. Computa-
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de Aperfeicoamento de Pessoal de Nvel Superior) for the doctoral Schmitt KD, Chu CT-W, Olson DH, Sheppard EW, McCullen
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