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A facile in situ pillaring methodthe synthesis of


Al-pillared montmorillonite
Yan Gao, Wenjie Li, Huimin Sun, Zaihang Zheng, Xuejun Cui, Hongyan Wang, Fanyu Meng
College of Chemistry, Jilin University, Changchun 130012, China
a b s t r a c t a r t i c l e i n f o
Article history:
Received 24 April 2013
Received in revised form 2 December 2013
Accepted 4 December 2013
Available online xxxx
Keywords:
Al-pillared-montmorillonite
In situ
PEG400
One step
A facile pillaring method for Al-pillared montmorillonite (Al-pillared-MMT) has been established by the in situ
formation polyoxocation [Al
13
O
4
(OH)
24
(H
2
O)
12
7+
] in the interlayer of montmorillonite (MMT). The result
of X-ray diffraction (XRD) showed that the pillaring effect was consistent with that of the traditional method
namely, the basal spacing was up to 18.8 . PEG400 in the synthesis system played a part of a layer extending
agent which could promote the forming of Al
13
7+
in the layer of MMT. The nitrogen adsorptiondesorption mea-
surement exhibited that the pore size and BET surface area of pillared montmorillonite(MMT) via an in situ way
were 3.55 nmand 181 m
2
/g, respectively. The BET surface area was larger than the conventional pillared MMT
and the pore size was nearly the same with traditional methods. The process of synthesis Al
13
7+
and pillaring MMT
were completed in one step in this method, which was a facile and effective method for preparing pillared MMT.
2013 Elsevier B.V. All rights reserved.
1. Introduction
Pillared interlayered clays (PILCs) have seen widespread application
in the elds of plant growth, pollutant transfer, nutrient cycling and pe-
troleum engineering (Bhattacharyya and Gupta, 2008; Brindley and
Sempels, 1977; Kanda et al., 2009; Kloprogge et al., 2005; Vardoulakis
et al., 2011) due to their highpermanent porosity, excellent thermal sta-
bility and catalytic feature (Gil et al., 2000, Kloprogge 1998;). Therefore,
more and more researchers have focused on the pillared interlayered
clays, such as Fe(III) pillared montmorillonite (Martin-Luengo et al.,
1989), mixed Al/Cu-pillared clays (Frini et al., 1997; Gil et al., 2000),
Al-Fe-pillared clay (Storaro et al., 1996), and Al-pillared montmorillon-
ite (Itadani et al., 2007; KhalaP et al., 1997; Kloprogge et al., 2002).
However, the most studied is Al-pillared montmorillonite (Al-pillared-
MMT), which not only possesses unique microporous structural charac-
teristics, excellent thermal stability and a large BET surface area as
an ideal catalyst supporting material, but also possesses a higher effec-
tive charge which is approximately +0.5 per Al exchanged with MMT
(Kloprogge, 1998).
The pillaring of MMT with Al
13
polyoxocation has been reported by
Vaughan in 19771981 (Vaughan et al., 1979; Vaughan and Lussier,
1980; Vaughan et al., 1981a, 1981b). Katdare et al. (1999, 2000) have
prepared Al-pillared-MMT by the ultrasonic-assisted method during
the cation exchange process. Fetter et al.(1997) have proposed a
pillaring method of microwave irradiation in order to shorten the time
of pillaring. Del Riego et al. (1994) have reported a route of the Al-
polyoxycations pillared interlayered clays (PILCs-Al) via dialysis bags.
Storaro et al. (1996) have attempted to pillar natural saponite, calcium
bentonite and laponite in acetone using solid chlorhydrol.
Based on the above-mentioned methods, pillared process includes
two parts of the pillared agent preparation process and pillared process.
In that way, it will consume a lot of time to prepare Al
13
7+
and need large
amounts of water during the cation exchange step (Aouad et al., 2005;
Fetter et al., 1997; Sivaiah et al., 2010). Therefore, it's signicant to
develop a facile preparation method of Al-pillared-MMT. As we know,
the Al
13
7+
is formed during the hydrolysis of aluminum salts in aqueous
solution (OH

/Al
3+
ratio 2.0 to 2.5) and it is composed of 13 aluminum
ions, in which, one with a tetrahedral coordination is surrounded by 12
with octahedral aluminum ions (Shi et al., 2007). And the hydrolysis
process has been obtained from
27
Al NMR studies (Kloprogge et al.,
1995). If this hydrolysis process occurs in the interlayer of montmoril-
lonite, Al-pillared-MMT will be prepared in situ by one-step.
A facile in situ pillaring method is developed for Al-pillared-MMT.
In this process, PEG400 is employed as the layer extending agent. The
Al-pillared-MMT is prepared using minimum expenditure of time and
water.
2. Experimental
2.1. Materials
The raw MMT was from Jilin in the Northwest of China (Xia et al.,
2010). The coarse particles were removed by sedimentation technique
for obtaining the host material for pillaring. AlCl
3
6H
2
O (Xilong
Chemical Reagent Company, China), NaOH (Beijing Chemical Reagent
Company, China) and the polyethylene glycol 400 (PEG400) (Beijing
Chemical Reagent Company, China) were of reagent grade. And the
water used was distilled by deionization.
Applied Clay Science xxx (2013) xxxxxx
Corresponding author at: College of Chemistry, Jilin University, Qianjin Street 2699#,
Changchun 130012, China. Tel./fax: +86 431 85168470.
E-mail address: mengfanyu@jlu.edu.cn (F. Meng).
CLAY-02864; No of Pages 5
0169-1317/$ see front matter 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.clay.2013.12.004
Contents lists available at ScienceDirect
Applied Clay Science
j our nal homepage: www. el sevi er . com/ l ocat e/ cl ay
Please cite this article as: Gao, Y., et al., Afacile insitu pillaring methodthe synthesis of Al-pillaredmontmorillonite, Appl. Clay Sci. (2013), http://
dx.doi.org/10.1016/j.clay.2013.12.004
2.2. Characterization techniques
The X-ray diffraction patterns of the clay materials were recorded on
a Rigaku D/MAX 2550 diffractometer equipped with Ni-ltered CuK

radiation ( = 0.154 nm) and operated at 40 kV and 40 mA with a


xed slit. The XRD measurements were carried out in the 2 range of
230 with a scan speed of 6/min.
Nitrogen adsorption experiments were performed using a static
volumetric apparatus (Micromeritics ASAP 2020 adsorption analyzer)
at 77 K. The weight of each sample was 0.16 g and the sample was
previously degassed for 24 h at 473 K. And the t-plot analysis was
used to character the surface area and microporosity of the prepared
sample (Gregg and Sing, 1982).
2.3. Synthesis of in situ Al
13
-pillared-montmorillonite
0.6060 g MMT powder was added into 30 ml 0.4 mol/L AlCl
3
6H
2
O
solution at 80 C and stirred continuously for 10 min. 5 ml PEG400
was added and stirred continuously for another 5 min. And then
69 mL 0.4 mol/L NaOH solutions were dropwise added slowly with
vigorous stirring. The nal ratio of [OH

]/[Al
3+
] was 2.3. After that,
stirring was needed for another 2 h. Then the solution was aged at
60 C for 24 h. The product was deposited for 0.5 h and dumped the
supernatant. The solid at the bottom was washed by distilled water
following a centrifugation at 10,000 revolutions per minute (rpm)
for 7 min, and this step was repeated 6 times until free of chloride.
The precipitate was dried at 60 C in drying oven, then rubbed into
powder, nally placed into a desiccator. This sample was denoted
as Al-(PEG)In-MMT. The Al-(No PEG)In-MMT prepared by the same
method, which was not added 5 ml PEG400. And the sample was
denoted as Al-MMT prepared by the conventional pillared method.
The detailed steps of the conventional pillared method and the in situ
pillared method were showed in Fig. 1.
3. Results and discussion
3.1. X-ray diffraction analysis
The XRD patterns of Al-MMT (conventional method), Al-(PEG)In-
MMT (in situ Al-pillared montmorillonite) and Al-(PEG)In-MMT after
calcinations under 400 C are showed in Fig. 2. The basal spacing of
Al-(PEG)In-MMT (Fig. 2c) is 18.8 , which is consistent with Al-MMT
(Fig. 2a) prepared by the conventional pillared method. Furthermore,
the basal (d
001
) peak is more symmetrical and intense in Al-(PEG)In-
MMT (Fig. 2c) than that of the Al-MMT (Fig. 2a). This phenomenon
demonstrates that the Al-(PEG)In-MMT possesses a more ordered or
higher crystallinity (Aouad et al., 2005; Fetter et al., 1997). The basal
spacing of Al-(PEG)In-MMT after calcinations under 400 C (Fig. 2b)
is 17.8 which is lower than that of Al-(PEG)In-MMT without calcina-
tions because of altering Al
13
to Al
2
O
3
during calcination, which also
proves that Al-(PEG)In-MMT does not collapse after calcinations
(Kloprogge, 1998). However, the in situ pillared process is easier than
conventional methods for the same effects.
3.2. Action of layer extending agent PEG400
The photos of PEG400, Al-(PEG)In-MMT and Al-MMT after calcina-
tions under 400 C are shown in Fig. 3(Up). From Fig. 3 (Up) we can
Fig. 1. The detailed step of the conventional pillared method (left) and the in situ Al-pillared montmorillonite (right).
2 Y. Gao et al. / Applied Clay Science xxx (2013) xxxxxx
Please cite this article as: Gao, Y., et al., Afacile insitu pillaring methodthe synthesis of Al-pillaredmontmorillonite, Appl. Clay Sci. (2013), http://
dx.doi.org/10.1016/j.clay.2013.12.004
see that the color of Al-MMT is brick-red after calcinations at 400 C.
However, the color of Al-(PEG)In-MMT is black which may be caused
by PEG400 carbonizing.
The XRD patterns of raw montmorillonite, PEG400 pillared montmo-
rillonite (PEG400-MMT), Al-(No PEG)In-MMT and Al-(PEG)In-MMT is
showed in Fig. 3 (Below). From Fig. 3 (Below) we can see that the basal
spacing (d
001
) of PEG400-MMT (Fig. 3a) is 14.6 (Chaiko, 2003) and
that of Al-(No PEG)In-MMT (Fig. 3b) is 16.4 . However, the basal
spacing (d
001
) of Al-(PEG)In-MMT (Fig. 3c) is 18.8 . This indicates that
the PEG400 as the layer extending agent can change the space of pillars,
which is useful for forming Al
13
O
4
(OH)
24
(H
2
O)
12
7+
in situ.
3.3. Adsorptiondesorption of nitrogen
The nitrogen adsorptiondesorption isotherms and BJH pore size
distribution of raw and pillared montmorillonite were presented in
Fig. 4. As could be observed fromFig. 4a, all of themare of the character
of type IV isotherms and a well-dened H
4
hysteresis loop in the IUPAC
classication (Gregg and Sing, 1982), which indicates that there are slit-
shapedpores inmontmorillonite andpillared montmorillonite. Further-
more, the pore size distribution (Fig. 4b) of pillared montmorillonite is
estimated at about 3555 by using BarrettJoynerHalenda (BJH)
from the adsorption isotherms, which is suitable as catalyst supporter.
The values of the BET surface area (m
2
/g) (S
BET
), micropore volume
(cm
3
/g), BJH adsorption cumulative volume and total pore volume
(cm
3
/g) are given in Table 1.
FromTable 1, we can see that the total pore volume and BJHadsorp-
tion cumulative volume of pores between a 17 and 3000 diameter
of Al-(PEG)In-MMT is larger than that of Al-MMT. While the micropore
volume of Al-MMT and Al-(PEG)In-MMT is almost similar. Therefore,
Fig. 2. XRD patterns of (a) Al-MMT, (b) Al-(PEG)In-MMT after calcinations under 400 C,
and (c) Al-(PEG)In-MMT.
Fig. 3. The appearance of PEG400, Al-(PEG)In-MMT and Al-MMT after calcinations
under 400 C (Up) and XRD patterns of (a) PEG400-MMT , (b) Al-(No PEG)In-MMT, and
(c)Al-(PEG)In-MMT (Below).
Fig. 4. Nitrogen adsorption-desorption isotherms and pore distribution of rawmontmoril-
lonite (), Al-MMT () and Al-(PEG)In-MMT ().
Table 1
The values of the BET surface area (m
2
/g)(S
BET
), micropore volume (cm
3
/g), BJH adsorp-
tion cumulative volume and total pore volume (cm
3
/g) for raw MMT and pillared MMT.
Clays S
BET
(m
2
/g)
Micropore
volume
(cm
3
/g)
BJH Adsorption cumulative
volume of pore between
17 and 3000 diameter
(cm
3
/g)
Total pore
volume
(cm
3
/g)
Raw MMT 20 0.0033 0.075 0.08
Al-MMT 144 0.0588 0.057 0.11
Al-(PEG)In-MMT 182 0.0484 0.129 0.17
3 Y. Gao et al. / Applied Clay Science xxx (2013) xxxxxx
Please cite this article as: Gao, Y., et al., Afacile insitu pillaring methodthe synthesis of Al-pillaredmontmorillonite, Appl. Clay Sci. (2013), http://
dx.doi.org/10.1016/j.clay.2013.12.004
we can conclude that the lager total pore volume is caused by mesopo-
rous and macroporosity which make Al-(PEG)In-MMT have a lager BET
surface area(S
BET
). Moreover, the nitrogen adsorptiondesorption iso-
therms at p/p
0
= 0.3 in Fig. 4a also shows that the nitrogen adsorbed
of Al-(PEG)In-MMT is higher than that of Al-MMT.
3.4. Formation mechanism of in situ Al-pillared montmorillonite
According to the characterization, the formation mechanism of Al-
(PEG)In-MMT can be concluded in the Fig .5.
Firstly, MMT and AlCl
3
6H
2
O solutions were mixed under stirring.
During that time, Al
3+
will exchange with cations in the MMT, then,
PEG400 extends ulteriorly the interlayer of MMT and increases the
basal spacing of MMT up to 14.6 . After that, the OH

as adjustment
agent of the pH, which forced the aluminum salts to hydrolyze in situ
in the interlayer of MMT. During the aging process, the oligomers of alu-
minum were formed, which lead to the reduction of charge in interlay-
er. The interlayer charge balance was achieved through the external
aluminum continuously diffusing into the interlayer, which made the
higher aluminum aggregates (Al
13
) form gradually in the interlayer
and the basal spacing of MMT was up to 18.8 . After calcinations, the
organic PEG400 altered into carbon and Al
13
and residue monomers
changed in to aluminum oxide. The nal basal spacing of the Al-In-
MMT-400 was 17.8 and the structure was steady.
4. Conclusions
This work reports a simple and rapid approach for the synthesis
of Al-pillared montmorillonite. PEG400 as layer extending agent
could change the condition of pillaring. X-ray diffraction (XRD) result
demonstrated the basal spacing of the Al-(PEG)In-MMT was up to
18.8 which was consistent with that of conventional pillar method
and indicated that Al
13
form in situ the interlayer of montmorillonite.
Furthermore, the result of the adsorption of nitrogen demonstrated
that the Al-(PEG)In-MMT possess larger BET surface area than the Al-
MMT and the same pore distribution with the Al-MMT. The nal basal
spacing of Al-(PEG)In-MMT after calcinations was 17.8 and the struc-
ture was steady. Except, the process of synthesis Al
13
7+
and pillaring
MMT was completed in one step in this method, which made industri-
alization come true easily.
References
Aouad, A., Mandalia, T., Bergaya, F., 2005. A novel method of Al-pillared montmorillonite
preparation for potential industrial up-scaling. Appl. Clay Sci. 28, 175182.
Brindley, G.W., Sempels, R.E., 1977. Preparation and properties of some hydroxy-
aluminium beidellites. Clay Miner. 12, 229237.
Bhattacharyya, G.G., Gupta, S.S., 2008. Adsorptionof a fewheavy metals onnatural and mod-
ied kaolinite and montmorillonite: a review. Adv. Colloid Interface Sci. 140, 114131.
Chaiko, D.J., 2003. Newpoly(ethylene oxide)-clay composites. Chem. Mater. 15, 11051110.
Del Riego, A., Herrero, I., Pesquera, C., Blanco, C., Benito, I., Gonza' lez, F., 1994. Preparation
of PILC-Al through dialysisbags: a comparative study. Appl. Clay Sci. 9, 189197.
Fetter, G., Heredia, G., Velzquez, L.A., Maubert, A.M., Bosch, P., 1997. Synthesis of
aluminum-pillared montmorillonites using highly concentrated clay suspensions.
Appl. Catal., A 162, 4145.
Frini, N., Crespin, M., Trabelsi, M., Messad, D., Van Damme, H., Bergaya, F., 1997. Prelimi-
nary results on the properties of pillared clays by mixed A1Cu solutions. Appl. Clay
Sci. 12, 281292.
Gil, A., GandA, L.M., Vicente, M.A., 2000. Recent advances in the synthesis and catalytic
applications of pillared clays. Catal. Rev. 42, 145212.
Gregg, S.J., Sing, K.S.W., 1982. Adsorption, Surface Area and Porosity. Academic Press,
London (1982).
Itadani, A., Tanaka, M., Abe, T., Taguchi, H., Nagao, M., 2007. Al-pillared montmorillonite
clay minerals: low-pressure CO adsorption at room temperature. J. Colloid Interface
Sci. 313, 747750.
Katdare, S.P., Ramaswamy, V., Ramaswamy, A.V., 1999. Ultrasonication: a competitive
method of intercalation for the preparation of alumina pillared montmorillonite
catalyst. Catal. Today 49, 313320.
Katdare, S.P., Ramaswamy, V., Ramaswamy, A.V., 2000. Factors affecting the preparation
of alumina pillared montmorillonite employing ultrasonics. Microporous Mesoporous
Mater. 37, 329336.
Kanda, Y., Iwamoto, H., Kobayashi, T., Uemichi, Y., Sugioka, M., 2009. Preparation of
highly active alumina-pillared clay montmorillonite-supported platinum catalyst
for hydrodesulfurization. Top. Catal. 52, 765771.
KhalaP, H., Bouras, O., Perrichon, V., 1997. Synthesis and characterization of Al-pillared
and cationic surfactant modied Al-pillared Algerian bentonite. Microporous Mater.
8, 141150.
Kloprogge, J.T., Diken, P.J., Jansen, J.B.H., Geus, J.W., 1995. One- and two-dimensional 27 Al
MAS-NMR study of basic aluminum sulfate. J. Non-Cryst. Solids 181, 151156.
Kloprogge, J.T., 1998. Synthesis of smectites and porous pillared clay catalysts: a review.
J. Porous. Mater. 5, 541.
Kloprogge, J.T., Evans, R., Leisel, H., Frost, R.L., 2002. Characterisation and Al-pillaring of
smectites from Miles, Queensland (Australia). Appl. Clay Sci. 20, 157163.
Kloprogge, J.T., Duong, L.V., Frost, R.L., 2005. A reviewof the synthesis and characterisation
of pillared clays and related porous materials for cracking of vegetable oils to produce
biofuels. Environ. Geol. 47, 967981.
Fig. 5. The formation mechanism of Al-(PEG)In-MMT.
4 Y. Gao et al. / Applied Clay Science xxx (2013) xxxxxx
Please cite this article as: Gao, Y., et al., Afacile insitu pillaring methodthe synthesis of Al-pillaredmontmorillonite, Appl. Clay Sci. (2013), http://
dx.doi.org/10.1016/j.clay.2013.12.004
Martin-Luengo, M.A., Martins-Carvalho, H., Ladriere, J., Grange, P., 1989. Fe(III)-pillared
montmorillonites: preparation and characterization. Clay Miner. 24, 495504.
Shi, B., Li, G., Wang, D., Tang, H., 2007. Separation of Al
13
from polyaluminum chloride by
sulfate precipitation and nitrate metathesis. Sep. Purif. Technol. 54, 8895.
Sivaiah, M.V., Petit, S., Brendl, J., Patrier, P., 2010. Rapid synthesis of aluminium
polycations by microwave assisted hydrolysis of aluminium via decomposition of
urea and preparation of Al-pillared montmorillonite. Appl. Clay Sci. 48, 138145.
Storaro, L., Lenarda, M., Ganzerla, R., Rinaldi, A., 1996. Preparation of hydroxy A1 and
A1/Fe pillared bentonites fromconcentrated clay suspensions. Microporous Mater. 6,
5563.
Vardoulakis, E., Karamanis, D., Assimakopoulos, M.N., Mihalakakou, G., 2011. Solar cooling
with aluminium pillared clays. Sol. Energy Mater. Sol. Cells 95, 23632370.
Vaughan, D. E. W., Lussier, R. J., Magee, J. S., 1979. Pillared interlayered clay materials
useful as catalysts and sorbents U.S. Patent, 4,176,090.
Vaughan, D.E.W., Lussier, R.J., 1980. Preparation of molecular sieves based on pillared
interlayered clays (PILC). Proceedings of the 5th International Conference on Zeolites.
Heyden, London, pp. 94101.
Vaughan, D. E. W., Lussier, R. J., Magee, J. S., 1981. Stabilized pillared interlayered clay. U.S.
Patent, 4,248,739
Vaughan, D. E. W., Lussier, R. J., Magee, J. S.,1981. Pillared interlayered clay products. U.S.
Patent, 4,271,043.
Xia, M.S., Jiang, Y.S., Zhao, L., Li, F.F., Xue, B., Sun, M.M., Liu, D.R., Zhang, X.G., 2010.
Wet grinding of montmorillonite and its effect on the properties of mesoporous
montmorillonite. Colloids Surf. A Physicochem. Eng. Asp. 356, 19.
5 Y. Gao et al. / Applied Clay Science xxx (2013) xxxxxx
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