Professional Documents
Culture Documents
a r t i c l e
i n f o
Article history:
Available online 5 June 2012
This article is dedicated to Prof. Dr. Jens
Weitkamp on the occasion of his 70th
birthday.
Keywords:
Mesoporous material
Acidity
Preparation
ZSM-5 nanoseeds
Characterization
a b s t r a c t
Ordered hexagonal mesoporous materials have been successfully synthesized in a two-step process from
assembly of pre-formed nanoscale ZSM-5 precursors at elevated temperature by pH adjusting during
synthesis. The resulting materials were characterized by small-angle X-ray scattering (SAXS), N2 adsorption and desorption (BET), transmission electron microscopy (TEM), temperature-programmed desorption of ammonia (NH3-TPD), FTIR spectroscopy of pyridine adsorptiondesorption (pyr-FTIR), atomic
absorption spectroscopy (AAS) and inductively coupled plasma-atomic emission spectroscopy (ICPAES). It was found out that a highly ordered mesoporous material with both improved hydrothermal stability and acidic properties can be optimally prepared at pH 3.5 and 200 C. The ordered mesostructure of
such material is well preserved even after steaming at 800 C for 4 h, with little loss in BET specic surface of 10.7% only, while its acidic properties are signicantly enhanced in terms of both acid strength and
total acidity. These improved properties can be attributed to the synergistic advantages of the use of zeolite nanoseeds, high temperature synthesis and pH adjustment.
2012 Elsevier Inc. All rights reserved.
1. Introduction
Ordered mesoporous materials, typically like MCM-41 [1] and
SBA-15 [2], have attracted considerable attention due to their potential application in catalysis and separation. Compared to microporous zeolites, which are widely used as industrial catalysts,
mesostructured materials with high surface areas and large, uniform pore sizes might overcome the diffusion limitation encountered in zeolite catalysis, being suitable for the conversion of
bulky molecules [3,4]. Unfortunately, these mesoporous materials
exhibit relatively weak acidity and poor hydrothermal stability
due to the amorphous nature of the mesopore walls, which severely hinder their practical uses [5].
Much effort has been devoted to improve both the poor acidity
and low hydrothermal stability of mesoporous molecular sieves
over the past two decades [69]. It has been demonstrated that
increasing the atomic order of the mesopore walls is an effective
strategy to enhance both the acidity and hydrothermal stability
[1013]. Kloetstra et al. [10] rst reported the Al-MCM-41 with
zeolitic structures in the mesopore walls, generated by partial crystallization of the pre-assembled amorphous walls of Al-MCM-41 in
the presence of microporous zeolite structure directors. However,
later studies [1113] have shown that this approach only allows
achieving low degrees of crystallinity, not higher than 42%. Further
Corresponding author. Fax: +49 381 1281 51246.
E-mail address: andreas.martin@catalysis.de (A. Martin).
1387-1811/$ - see front matter 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.micromeso.2012.05.036
121
structures [25,26]. To understand such an effect in the present synthesis, the particle size of the seeds in the precursor solution was
determined by SAXS. Fig. 1 shows the scattering pattern with vector q of the ZSM-5 precursor solution after aging at 90 C for 6 h.
The pattern reects scattering from two populations. The scattering intensity observed between 0.5 nm1 < q < 6 nm1 is attributed
to the presence of small primary ZSM-5 units. At low q values, a
steeply increasing intensity in scattering is observed, which reects the presence of larger ZSM-5 units. Guinier analysis [27]
was applied to obtain information about the particle size of the different populations. For the primary ZSM-5 units, a Guinier radius
(Rg) of 2.4 nm was determined. The Rg for the larger structures
amounted to 14.4 nm. The parameter Rg has a model dependent
relation to the size of the particles. Assuming spherical particle
shape, its radius RG can be calculated using the following equation:
Rg2 = (3/5) RG2. From the presented data, it is reasonable to conclude that the ZSM-5 precursor solution contains the primary units
and their aggregates, which are presumed to promote the zeolite
nucleation to form ZSM-5 crystals. These results are consistent
with previous reports [2830].
100
110
200
122
(a)
(b)
(c)
(d)
(e)
0.5
1.0
1.5
2.0
2.5
2 Theta/degree
Fig. 2. SAXS patterns with 2h of (a) SAZ_1.5; (b) SAZ_2.5; (c) SAZ_3.5; (d) SAZ_4.5;
(e) SAZ_5.5.
A
(a)
3
(b)
(c)
(d)
(e)
0.0
0.2
0.4
0.6
0.8
1.0
Rg = 14.4 nm
Rg = 2.4 nm
(a)
(b)
(c)
(d)
(e)
12
16
20
q/nm
-1
123
Fig. 4. TEM images of SAZ_3.5 viewing along [100] (A) and [110] (B) directions.
Table 1
Structural and textural properties of SAZ_x (x = 1.55.5).
Sample
D100 (nm)
a0 (nm)
Dp (nm)
W (nm)
SBET
(m2/g)
Vt
(cm3/g)
SAZ_1.5
SAZ_2.5
SAZ_3.5
SAZ_4.5
SAZ_5.5
11.13
11.14
11.18
11.15
11.13
12.85
12.86
12.91
12.87
12.85
9.0
9.1
9.1
9.1
3.85
3.76
3.80
3.77
424
412
372
297
184
1.05
1.10
0.97
0.80
0.77
a0: unit cell parameter (a0 = 2 d100/31/2); Dp: pore diameter; W: pore wall
thickness (W = a0 Dp); Vt: total pore volume.
unit cell of the SAZ_x samples seems to be not affected by the httpH.
The data of N2 adsorption/desorption are also in accordance
with those of SAXS. The samples SAZ_x (x = 1.53.5) show differing
textural properties compared to the two other ones (x = 4.55.5)
(Fig. 3, Table 1). As depicted in Fig. 3A, all SAZ_x samples exhibit
type IV isotherms with H1-type hysteresis loop, conrming their
mesoporous nature. However, the capillary condensation steps of
SAZ_1.5, SAZ_2.5 and SAZ_3.5 are very steep and occur in the relative pressure (p/po) range of 0.70.9, which is characteristic for an
ordered mesoporous material with a large and uniform pore size.
The two other samples (SAZ_4.5, SAZ_5.5) display a less steep hysteresis loop being indicative for a disordered mesostructure. The
dimension and uniformity of mesopores can be directly reected
by the pore size distribution (Fig. 3B). With the increase of pH values used in the hydrothermal treatment, the pore size distribution
of SAZ_x becomes broader. The pore size of the rst four samples
(x = 1.54.5) is about 9.09.1 nm, larger than that of MAS-9 [20]
prepared at a lower temperature (100 C), implying that the silica
based walls of these samples have been further condensed under
the hydrothermal treatment at high temperature, being similar
to the previous reports [31,34,35]. For SAZ_5.5, the mesopore system has been partially destroyed; therefore, its pore size cannot be
calculated. The disordered mesostructure of SAZ_4.5 and SAZ_5.5 is
also evidenced by their relatively low surface areas and pore volumes compared to those of the three other samples. As summarized in Table 1, SAZ_1.5, SAZ_2.5 and SAZ_3.5 show BET specic
surface areas ranging from 424 to 372 m2/g and pore volumes from
1.10 to 0.97 cm3/g, while these textural parameters reduce to
279 m2/g and 0.80 cm3/g for SAZ_4.5 and 184 m2/g and 0.77
ce:hsp sp="0.25"/>cm3/g for SAZ_5.5. Hence, in order to obtain ordered mesoporous materials, the htt-pH value should not be higher
than 3.5. According to Pan et al. [31], at higher pH values the surfactantsilanol interaction becomes weak, leading to the decline of
the surfactant content adsorbed within the pores. As a result, the
mesostructure partially collapsed while the framework shrinkage
occurred at elevated temperature (200 C).
124
Intensity / a.u.
Intensity / a.u.
(a)
(b)
(c)
(a)
(b)
(d)
(c)
(d)
(e)
100
100
200
300
400
500
200
600
Temperature /C
Fig. 5. NH3-TPD proles of (a) SAZ_1.5; (b) SAZ_2.5; (c) SAZ_3.5; (d) SAZ_4.5; (e)
SAZ_5.5.
300
400
500
600
Temperature / C
Fig. 6. NH3-TPD prole of (b) SAZ_3.5 compared to those of (a) HZSM-5, (c) Al-SBA15, and (d) SBA-15.
Table 2
Acidity of SAZ_x (x = 1.55.5), Al-SBA-15, H-ZSM-5 and SBA-15.
Sample
Si/Al ratio in
gel
Si/Al ratio in
productsd
SAZ_1.5
SAZ_2.5
SAZ_3.5
SAZ_4.5
SAZ_5.5
Al-SBA-15a
HZSM-5b
SBA-15c
30
30
30
30
30
30
40
1
67
40
34
32
29
45
n.a.
1
0.16
0.22
0.26
0.27
0.35
0.18
1.04
a
Synthesized by the same procedure as SAZ_3.5, but using the conventional silica
based source.
b
Synthesized according to the patent of Kulkarni et al. [24].
c
Prepared by the original recipe of Zhao et al. [2].
d
Si, Al content in the products analyzed by AAS and ICP, respectively.
Fig. 7. FTIR spectra of pyridine desorption of SAZ_3.5 at various temperatures (L-Py Lewis sites, PyH+ - Bronsted sites).
From the point of view of acid strength, Fig. 5 shows that all samples exhibit two ammonia desorption peaks. The rst sharp peak
around 200 C can be attributed to weak acid sites, while the broader peak in the range of 350450 C shows the presence of medium
and strong acid sites. However, it seems that the acid strength of
SAZ_x samples is dominated by weak and medium sites and still
lower than that of HZSM-5 crystals, but higher than that of AlSBA-15 prepared from conventional silica based precursors under
the same conditions in terms of both acid strength and total acidity.
The pure SBA-15, as expected, exhibits signicantly less response,
which is indicative of little or no acid sites present (Table 2, Fig. 6).
In addition, the nature of the acid sites in the representative sample SAZ_3.5 was evaluated by pyridine adsorption/desorption. The
pyr-FTIR spectra are shown in Fig. 7. After evacuation at various temperatures (100400 C), the spectra of pyridine desorption show
two bands at 1543 cm1 and 1451 cm1 which are characteristic
for Brnsted and Lewis acid sites, respectively. Furthermore, these
two bands are still present at 400 C, indicating the presence of both
strong Brnsted and Lewis acid sites in the solid sample. The nature
and mechanism of formation of the Lewis sites are not fully clear, but
these kinds of acidity could be generated from either extra framework aluminum species, such as AlO5 and AlO6, or defect sites such
as AlO3 or both [37]. Notably, while the strong Lewis acid sites are
often observed in zeolites and mesoporous aluminosilicates, the
strong Brnsted acid sites are only typical for zeolites [13,36,38].
The presence of strong Brnsted acid sites in SAZ_3.5 can be
125
100
100
110
200
(a)
100
110
200
(a)
110
200
(b)
(b)
0.5
1.0
1.5
2.0
2.5
0.5
1.0
2 Theta/degree
1.5
2.0
2.5
2 Theta/degree
Fig. 8. SAXS patterns of SAZ_3.5 (A) and SBA-15 (B): (a) before and (b) after steam treatment at 800 C for 4 h.
4. Conclusions
Ordered hexagonal mesoporous materials with greatly improved hydrothermal stability and total acidity have successfully
been synthesized by assembly of pre-formed ZSM-5 precursors at
high temperature (200 C) by pH adjusting method. The optimal
hydrothermal treatment pH was found to be 3.5 under the studied
conditions. It was shown that the material prepared at pH 3.5
(SAZ_3.5) possesses a highly ordered mesostructure with remarkable hydrothermal stability and increased acidity. The ordered
mesostructure of SAZ_3.5 is well maintained after steam treatment
Table 3
Textural properties of SAZ_3.5 and SBA-15 before and after steaming at 800 C for 4 h.
Sample
SAZ_3.5
Calcined
Steamed
SBA-15a
Calcined
Steamed
a
Dp (nm)
Vt (cm3/g)
SBET (m2/g)
9.1
9.1
0.97
0.82
372
332
10.7
6.4
4.6
1.06
0.43
879
308
64.9
Acknowledgments
The authors would like to thank Dr. U. Bentrup for pyr-FTIR
measurements, Dr. M.-M. Pohl for TEM images; Mr. R. Eckelt for
N2 adsorption and desorption studies. Dr. Hoang is also acknowledged for his help to access NH3-TPD measurement. X.-H. Vu
thanks the government of Vietnam and LIKAT for the nancial
support.
800
700
A
Volume absorbed (cm3/g)
700
600
500
400
300
200
100
0
0.0
(a)
600
500
400
300
(a)
200
100
(b)
(b)
0.2
0.4
0.6
0.8
1.0
0
0.0
0.2
0.4
0.6
0.8
1.0
Fig. 9. N2 sorption isotherms of SAZ_3.5 (A) and SBA-15 (B): (a) before and (b) after steam treatment at 800 C for 4 h.
126
References
[1] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Leonowicz, C.T. Kresge, K.D. Schmitt, C.T.W.
Chu, D.H. Olson, E.W. Sheppard, J. Am. Chem. Soc. 114 (1992) 1083410843.
[2] D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D. Stucky,
Science 279 (1998) 548552.
[3] A. Corma, Chem. Rev. 97 (1997) 23732419.
[4] Y. Wan, D. Zhao, Chem. Rev. 107 (2007) 28212858.
[5] R. Chal, C. Grardin, M. Bulut, S. van Donk, ChemCatChem 3 (2011) 6781.
[6] Y. Liu, T.J. Pinnavaia, J. Mater. Chem. 12 (2002) 31793190.
ejka, S. Mintova, Catal. Rev. 49 (2007) 457509.
[7] J. C
[8] K. Egeblad, C.H. Christensen, M. Kustova, C.H. Christensen, Chem. Mater. 20
(2008) 946960.
[9] F. Chen, X. Meng, F. Xiao, Catal. Survey Asia 15 (2011) 3748.
[10] K.R. Kloetstra, H. van Bekkum, J.C. Jansen, Chem. Commun. (1997) 22812282.
[11] A.A. Campos, L. Dimitrov, C.R. da Silva, M. Wallau, E.A. Urquieta-Gonzlez,
Microporous Mesoporous Mater. 95 (2006) 92103.
[12] M.J. Verhoef, P.J. Kooyman, J.C. van der Waal, M.S. Rigutto, J.A. Peters, H. van
Bekkum, Chem. Mater. 13 (2001) 683687.
[13] D.T. On, S. Kaliaguine, Angew. Chem., Int. Ed. 40 (2001) 32483251.
[14] Y. Liu, W. Zhang, T.J. Pinnavaia, J. Am. Chem. Soc. 122 (2000) 87918792.
[15] Y. Liu, W. Zhang, T.J. Pinnavaia, Angew. Chem., Int. Ed. 40 (2001) 12551258.
[16] Y. Liu, T.J. Pinnavaia, J. Mater. Chem. 14 (2004) 10991103.
[17] Z. Zhang, Y. Han, F. Xiao, S. Qiu, L. Zhu, R. Wang, Y. Yu, Z. Zhang, B. Zou, Y.
Wang, H. Sun, D. Zhao, Y. Wei, J. Am. Chem. Soc. 123 (2001) 50145021.
[18] C.W. Ingram, Y. Ghirmazion, T. Mehreteab, J. Porous Mater. 14 (2007) 717.
[19] Y. Han, F.-S. Xiao, W. Wu, Y. Sun, X. Meng, D. Li, S. Lin, F. Deng, X. Ai, J. Phys.
Chem. B 105 (2001) 79637966.
[20] Y. Han, S. Wu, Y. Sun, D. Li, F.-S. Xiao, Chem. Mater. 14 (2002) 11441148.
[21] Y. Liu, T.J. Pinnavaia, Chem. Mater. 14 (2002) 35.
[22] F.-S. Xiao, Top. Catal. 35 (2005) 924.
[23] X. Meng, F. Nawaz, F.-S. Xiao, Nano Today 4 (2009) 292301.