Catalysis Today 227 (2014) 33–36

Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Effectiveness of the tetramethylammonium size-modifier

in the synthesis of faujasite nanocrystals
Rachida Benabdallah Benarmas a,b , Abdelkader Bengueddach b , Francesco Di Renzo a,∗
a
Institut Charles Gerhardt Montpellier, UMR 5253 CNRS-UM2-ENSCM-UM1, Matériaux Avancés pour la Catalyse et la Santé, ENSCM, 8 rue de l’Ecole
Normale, 34296 Montpellier Cedex 5, France
b
Laboratoire de Chimie Des Matériaux, Université Oran Es-Senia, BP 1524, Oran El M’naouer, Algeria

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

Article history: This paper reports the effects of alkalinity, Si/Al ratio and amount of tetramethylammonium (TMA) on
Received 1 July 2013 the formation of nanocrystals of faujasite. The presence of TMA allows to form faujasite crystals smaller
Received in revised form than 0.1 ␮m. In a wide range of composition, there is no proportionality between the concentration of
29 September 2013
TMA in the synthesis system and the size of the zeolite crystals formed. TMA concentrations as low as
Accepted 11 November 2013
Available online 16 December 2013
0.05 mmol L−1 are enough to induce the formation of crystals of 30 nm. The role of TMA in the formation
of nanocrystals corresponds to a shift of the balance between nucleation and growth kinetics due to the
adsorption of organics at the surface of the nuclei of zeolite. The field of composition of the faujasite
Keywords:
Crystal size crystals shifts from zeolite Y to zeolite X according to the alkalinity of the synthesis system. As expected,
Zeolite X the effectiveness of silicon incorporation decreases with the alkalinity of the synthesis system. However,
Zeolite Y the effectiveness of silicon incorporation significantly increases with the content of TMA, suggesting that
Tetramethylammonium the large TMA cations contrast the depolymeryzing effect of alkalinity on the silicate species implied in
Faujasite the formation of the zeolite. This effect is modulated by the concentration of silicate in the synthesis
system.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction
The formation of nanocrystals of zeolites is a challenge with
wide implications on the accessibility of active sites and on the dif-
fusion paths in adsorption and catalysis. It was early realized that
the decrease of crystal size can improve the efficiency of zeolite cat-
alysts, be they used as single crystals [1] or embedded in a matrix
[2]. The conditions of synthesis of nanocrystalline zeolites, with
crystal sizes lower than 100 nm, have been extensively reviewed
[3,4]. In the case of faujasite, the zeolite at the basis of most zeolite
industrial catalysts and sorbents, Schoeman et al. [5] showed that
the formation of nanocrystals was made possible by the use of large
amounts of tetramethylammonium (TMA) cations in the synthesis
system. After this seminal paper, the formation of nanocrystals of
faujasite in the presence of TMA was successfully implemented by
several research groups [6–12].
An additional advantage of the use of alkylammonium cations
in the synthesis of zeolites is that, due to their size larger than alkali
cations, they allow to form zeolites with a higher Si/Al ratio. This is
potentially useful in the formation of faujasite for catalytic applica-
tions, as zeolite Y (faujasite with Si/Al 2.5) is more hydrothermally
∗ Corresponding author. Tel.: +33 607508148/33 467163479; fax: +33 467163470.
E-mail address: direnzo@enscm.fr (F. Di Renzo).
stable than zeolite X (Si/Al lower than 1.5) [13]. However, TMA,
as other organic templates, is non-recyclable and relatively expen-
sive, and its use in large amount as a dispersing agent is a significant
drawback of the procedure. Some increase of the TMA yield in the
synthesis of zeolite Y has been achieved by recycling the mother
liquor in a series of successive syntheses [14]. The formation of
nanocrystals of faujasite in the absence of organic agents has been
attempted by introducing an ageing step in the preparation of the
synthesis batch [15]. This approach has allowed to form crystals of
faujasite with a size of 146 nm and a Si/Al ratio 1.86 or crystals with
a size of 35 nm and Si/Al 1.48.
The aims of the present work are to investigate the role of TMA
in the formation of nanocrystalline faujasite and to search for eco-
nomically viable conditions of formation of nanocrystalline zeolites
X and Y. To achieve this target, a study was carried out on the crys-
tallization of faujasite from synthesis batches of different alkalinity,
Si/Al ratio and TMA content.
2. Materials and methods
The reagents used for the synthesis of faujasite nanocrystals
were Ludox HS-40 colloidal silica from Sigma-Aldrich (40 wt% sus-
pension in water), sodium aluminate from Carlo Erba (36.6 wt%
Na2 O, 50.3 wt% Al2 o3 ), sodium hydroxide Prolabo, tetramethylam-
monium (TMA) bromide and hydroxide (25 wt% aqueous solution)

0920-5861/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cattod.2013.11.007
34 R.B. Benarmas et al. / Catalysis Today 227 (2014) 33–36

Fig. 1. Scanning electron micrograph of aggregates of crystals of zeolites Y (Si/Al 2.1,

lefthand) and X (Si/Al 1.5, righthand) formed from synthesis batches with TMA/Si
0.15.

from Aldrich, and deionized water. Faujasite crystals were formed

from synthesis gels in the field of molar composition Na/Al 2.26–10, Fig. 2. Transmission electron micrograph of the cross-section of an aggregate of
TMA/SiO2 0.09–1.37, Al/SiO2 0.13–0.46, H2 O/SiO2 9–36. The alka- crystals of faujasite (Si/Al 1.8, formed from a synthesis batch with TMA/Si 0.10).
linity of the synthesis system was defined as the molar ratio
OH− /Si = (Na + TMA–Al–Br)/Si. Sodium aluminate and silica were
added to a stirred TMA-containing alkaline solution. The result- 10000
ing gel was aged for 24 h at room temperature and then put in a

crystal size (nm)

steel vessel at 90–100 ◦ C for 72 h. Different times and temperature
were used in the case of individually specified literature synthe- 1000
ses. The material resulting after crystallisation was precipitated by
centrifugation, washed with deionized water up to pH 9, and dried
overnight at 80 ◦ C. 100
The solids formed were characterized by powder X-ray diffrac-
tion ((Bruker AXS D-8 diffractometer with Cu K␣ radiation),
scanning (Hitachi S-4800 microscope) and transmission (JEOL 1200 10
0.0 0.5 1.0 1.5
EX II) electron microscopy and EDX analysis (Hitachi S-4500). The gel alkalinity (OH-/SiO2)
effect of crystal size on XRD line broadening was determined by
Williamson-Hall plots. The amount of organics in the zeolite was Fig. 3. Size of faujasite crystals as a function of the alkalinity of the synthesis system.
evaluated by thermal gravimetric analysis in air flow (Perkin Elmer Syntheses in the absence of organics (triangles) and in the presence of TMA with
STA 6000). TMA/Si ratio higher than 1 (filled circles) or not higher than 0.18 (void circles).

3. Results
In Table 1 the composition of synthesis batches and the com-
position and size of faujasite formed from literature syntheses in
the absence of TMA or in the presence of large amounts of TMA are
reported, together with the corresponding data for original synthe-
ses of faujasites formed in the presence of small amounts of TMA.
The data of Table 1 clearly indicate that the presence of TMA allows
to obtain faujasite crystals smaller than about 0.1 ␮m. However, it
seems also clear that it is possible to form crystals of this small size
also in the presence of amounts of TMA much smaller than TMA/Si
ratio higher than 1 reported in the literature.
Scanning electron micrographs of faujasites formed in the
presence of small amounts of TMA are reported in Fig. 1. The
nanocrystals of zeolite X or Y recovered from centrifugation are
aggregated in irregular lumps. The size and composition of the crys-
tals depend on the synthesis conditions and are especially affected
by the alkalinity, the Si/Al ratio and the TMA content of the synthesis
batches.
The microstructure of the material was elucidated by trans-
mission electron microscopy (TEM). TEM of the cross-section of
a typical aggregate is shown in Fig. 2. Individual nanocrystals with
size from 30 to 70 nm presents repeating modules in good agree-
ment with the 111 spacing of faujasite.
In Fig. 3, the size of faujasite crystals formed in the presence of
different amounts of TMA is presented as a function of the alka-
linity of the synthesis system. In the case of zeolite Y formed in
the absence of TMA [16,17], crystals in the micrometer size range
are formed. Crystal size decreases at increasing alkalinity of the
synthesis batch, as frequently observed in zeolite synthesis [18]. In
the presence of TMA, smaller crystals are formed, in the size range
30–120 nm. It can be remarked that synthesis with TMA/Si ratio
higher than 1 and lower than 0.18 produce crystals in the same

Table 1
Composition of synthesis batches and properties of zeolite formed.

Synthesis batch composition Synthesis alkalinity Zeolite dry composition Crystal size (nm)

0.68 Na/0.20 Al/Si/16 H2 O [16] 0.48 NaAl(SiO2 )2.6 2400

1.11 Na/0.09 Al/Si/20 H2 O [17] 1.02 NaAl(SiO2 )2.2 500
0.01 Na/1.10 TMA/0.46 Al/Si/57 H2 O [9] 0.67 Na0.46 TMA0.54 Al(SiO2 )2.35 120
0.01 Na/1.66 TMA/0.46 Al/Si/57 H2 O [9] 0.67 Na0.40 TMA0.60 Al(SiO2 )2.37 37
0.90 Na/1.37 TMA/0.23 Al/Si/31 H2 O 1.61 Na0.90 TMA0.10 AlO2 (SiO2 )1.54 70
0.92 Na/0.15 TMA/0.41 Al/Si/32 H2 O 0.51 Na0.967 TMA0.033 AlO2 (SiO2 )2.1 50
1.23 Na/0.10 TMA/0.20 Al/Si/24 H2 O 1.03 Na0.971 TMA0.029 AlO2 (SiO2 )1.8 40
1.76 Na/0.15 TMA/0.41 Al/Si/32 H2 O 1.36 Na0.963 TMA0.037 AlO2 (SiO2 )1.57 32
1.96 Na/0.18 TMA/0.44 Al/Si/36 H2 O 1.51 Na0.963 TMA0.037 AlO2 (SiO2 )1.50 38
 R.B. Benarmas et al. / Catalysis Today 227 (2014) 33–36
3
2.5
Si/Al zeolite
2 0.50
1.5
1
0.00 0.50 1.00 1.50 2.00
gel alkalinity (OH-/SiO2)
Fig. 4. Composition of zeolite as a function of the alkalinity of the synthesis system.
Syntheses in the absence of organics (triangles) and in the presence of TMA with
TMA/Si ratio higher than 1 (filled circles) or not higher than 0.18 (void circles).
1.00
Si yield / Al yield
0.50
0.00
0.00 0.50 1.00 1.50 2.00
gel alkalinity (OH-/SiO2)
Fig. 5. Effectiveness of silicon incorporation as a function of the alkalinity of the
synthesis system. Syntheses in the absence of organics (triangles) and in the pres-
ence of TMA with TMA/Si ratio higher than 1 (filled circles) or lower than 0.18 (void
circles).
size range. Moreover, in the presence of any amount of TMA, the
crystal size shows no clear dependence on the alkalinity.
The presence of TMA affected the composition of the zeolites
formed, as shown in Fig. 4, in which the Si/Al ratio of the zeo-
lites is reported as a function of the alkalinity of the synthesis
batch. The composition of the nanocrystals of faujasite formed
with low amounts of TMA spanned from Si/Al 2.1, corresponding
to a slightly aluminium-rich zeolite Y, to 1.36, corresponding to
a slightly silicon-rich zeolite X. In a general way, the Si/Al of the
zeolite decreased at increasing alkalinity of the synthesis batch, in
good agreement with the well-known decrease of the polymeri-
sation of silica at high alkalinity [19]. The data of Fig. 4 suggests
that, for a given alkalinity of the synthesis batch, the presence of
TMA decreases the Si/Al ratio of the zeolite formed. This behaviour
is clearly contradictory with the expected effect of a large organic
cation, which should bring about an increase of the Si/Al ratio. The
observed trend is indeed an artifact due to the simultaneous change
of several parameters of the synthesis. Alkalinity is not the only
parameter which affects the properties of the zeolite formed. In
order to achieve a given Si/Al ratio in the final zeolite, the Si/Al of
the synthesis batch is at least as important as the alkalinity and
the nature of the charge-compensating cation. In the synthesis of
zeolite Y in the absence of TMA, the desired Si/Al ratio near to 2.5
can only be attained in the presence of a large excess of silica in the
synthesis batch.
The effectiveness of incorporation of silicon can be expressed
as the ratio between the yields of incorporation of silicon and alu-
minium, corresponding to the ratio between the Si/Al ratios of the
zeolite and the synthesis batch. The effectiveness of incorpora-
tion of silicon is reported in Fig. 5 as a function of the alkalinity
of the synthesis batch. For a given TMA content (null, lower than
TMA/Si 0.18, higher than TMA/Si 1), the effectiveness of silicon
35
1.00
Si yield / Al yield
0.00
0 2 4 6 8 10 12
Si/Al synthesis
Fig. 6. Effectiveness of silicon incorporation as a function of the composition of
the synthesis system. Syntheses in the absence of organics (triangles) and in the
presence of TMA with TMA/Si ratio higher than 1 (filled circles) or lower than 0.18
(void circles).
incorporation decreases with the increase of alkalinity. This effect
corresponds to the lower degree of oligomerisation of silica in the
more alkaline systems, leading to the statistical incorporation of
less silica units between two aluminate groups [20]. The data of
Fig. 5 suggest that, at a given alkalinity, the effectiveness of silicon
incorporation increases with the amount of TMA in the synthesis
batch. This trend is in good agreement with the expected effect of
the replacement of sodium by TMA cations. It can be observed that
this effect is somewhat blurred in the high-alkalinity region of Fig. 5.
The rationale for this phenomenon relies on another parameter
affecting the effectiveness of incorporation of silicon.
The effectiveness of silicon incorporation is reported in Fig. 6 as
a function of the Si/Al ratio of the synthesis batches. For all synthe-
ses giving rise to faujasite, the effectiveness of silicon incorporation
decreases at increasing Si/Al of the synthesis batch following a same
hyperbolical trend. This trend, which corresponds to a virtually lin-
ear correlation between effectiveness of silicon incorporation and
Al/Si ratio of the synthesis batch, indicates that a law of diminishing
return is established between the amount of silica in the synthesis
system and the incorporation of silica in the zeolite. This effect is
quite logical, when it is considered that synthesis batches with a
Si/Al ratios as high as 11 can form a zeolite with inherent Si/Al ratio
of 2.5 only at a very low effectiveness of silicon incorporation. Such
a high Si/Al ratio in the synthesis batch can be needed to selectively
form zeolite Y in the absence of TMA. The trend of the data of Fig. 6
can be better understood by taking into account that the syntheses
have been carried out at different alkalinities and amounts of TMA,
in order to provide the conditions for the formation of faujasite
instead of other zeolites. In the absence of TMA or at low TMA/Na
ratios, the formation of gismondine can be avoided only by a high
alkalinity of the synthesis batch, with a corresponding decrease of
the effectiveness of silicon incorporation and the need for a high
Si/Al in the synthesis batch At very low Si/Al ratios of the synthesis
batches, the formation of sodalite has also to be avoided.
4. Discussion
The formation of faujasite in Na–TMA systems was early
observed, for instance as a metastable phase in the first steps of
synthesis of zeolite omega [21,22]. Indeed, the tetramethylammo-
nium cation is an effective template for the formation of sodalite
cages [23], the main structural units of faujasite. The competition
between TMA and sodium cation as templates of faujasite seems to
be at the basis of most methods of synthesis of faujasite nanocrys-
tals [5–9]. In these published methods, the ratio between TMA and
sodium in the synthesis batches varied from 23 [7] to 75 [9]. This
large excess of TMA did not correspond to an equivalent TMA/Na
ratio in the zeolite formed. TMA/Na ratios of 50 and 75 brought to
zeolite Y of TMA/Na ratios 1.19 and 1.48, respectively. Albeit much
lower than the ratios in the synthesis batch, these TMA levels in the
36 R.B. Benarmas et al. / Catalysis Today 227 (2014) 33–36
zeolite were more than the amount needed to completely fill the
sodalite cages of the faujasite structure. A clear effect of the partial
replacement of a small alkali cation by a large organic cation was a
rise of the Si/Al ratio of the zeolite. A typical example of this effect
can be observed in the case of the sodalite structure, which Si/Al
ratio is shifted from 1 in hydroxysodalite to 5 in tsaregorodsevite,
the natural TMA-sodalite, in correspondence with the replacement
of three hydrated sodium cations by one tetramethylammonium
cation.
A similar effect can be observed in the synthesis of faujasite in
the presence of TMA. The composition of faujasite is affected by
several parameters of the synthesis. The effectiveness of incorpo-
ration of silicate species decreases with the alkalinity and with the
silica content of the synthesis system, as shown in Figs. 5 and 6.
Despite the superposition of the effects of several parameters, the
data reported in Fig. 5 indicate that the effectiveness of incorpora-
tion of silicate species in the zeolite increases with the amount of
TMA in the synthesis system.
Beyond its effect on the Si/Al ratio of the zeolite formed, the TMA
cation has also a clear effect on the size of the crystals. As shown
in Fig. 3, the presence of TMA favours the formation of crystals of a
size between 30 and 100 nm, significantly smaller than the crystals
formed in the absence of organic cations. It has been remarked that
the synthesis of nanosized zeolites is a model system for the study
of processes of crystal growth [24]. From this point of view, it is clear
that the presence of TMA increases the ratio between the rate of
nucleation and the rate of growth of the crystals of faujasite, with a
corresponding decrease of crystal size. It can be observed that TMA
plays a similar role in the synthesis of zeolite alpha, whose crystals
are commonly smaller than the crystals of zeolite A synthesized
with Na as the only cation [25,26].
A tempting hypothesis would be that TMA, as an effective tem-
plate for sodalite cages, favours the formation of nuclei of faujasite.
However, a positive effect of TMA on the formation of the fauja-
site structure seems to be excluded by the partition coefficients
between TMA and Na cations during the synthesis. The composi-
tion data reported in Table 1 indicate that the incorporation of TMA
in the zeolite is much less effective that the incorporation of Na
cations. The partition coefficient (TMA/Na)zeolite /(TMA/Na)synthesis
varies from 0.01 for the syntheses with an excess of TMA to 0.4 for
the syntheses with the lowest amounts of TMA. In any case, Na is
the preferred cation for the synthesis. This suggest that TMA is less
efficient than Na in the formation and assembling of the building
blocks of faujasite, rendering quite unlikely that its presence plays
a positive role in the nucleation.
An alternative way to increase the ratio between nucleation rate
and growth rate is to decrease the growth rate of the crystals. A
negative effect of TMA on the assembling of building blocks could
indeed provide such a result. It is interesting to remark that, as
shown in Fig. 3, the size of nanocrystals of faujasite is not propor-
tional to the amount of TMA present in the synthesis system. The
independence of the effect on crystal size from the concentration of
TMA indicates that a limited amount of TMA is enough to affect the
crystal size of faujasite. This could suggest that the growth rate is
affected by the TMA cations adsorbed at the surface of the growing
nuclei more than by the amount of TMA incorporated in the zeolite.
This behaviour seems in agreement with a poisoning by TMA of the
surface of the growing crystals, with a corresponding decrease of
the growth rate.
The formation of nanocrystals at low TMA content has a clear
practical interest, as syntheses with a TMA/Si ratio not higher than
0.15 allows to form 40 nm crystals which contain no more than 4
TMA cations per 100 Na cations. The amount of TMA in the final
product is so low that removal of organics by thermal treatment
could not be required for several applications. Moreover, in the
presence of large excess of sodium, the yield of incorporation of
TMA cations is very low. This phenomenon opens the way to the
recycling of the organic-rich mother liquor collected at the end of
the synthesis [14].
5. Conclusions
The size of the crystals of faujasite is affected by several syn-
thesis parameters. In the absence of organics, the alkalinity of the
synthesis medium contributes to decrease the size of faujasite crys-
tals but induces the formation of Al-rich zeolite X. The use of TMA
as an organic modifier of the synthesis induces two effects: an
increase of the effectiveness of silicate incorpation in the zeolite
and a large decrease of the crystal size. Crystals of zeolite X and
Y between 30 and 100 nm are formed at very different concentra-
tions of TMA in the synthesis system. The proportionality between
the amount of TMA and the incorporation of silicate indicates that
the large organic cation plays a structural role in the increase of
the Si/Al of the zeolite. At variance with this effect, the influence
of TMA on the crystal size is not proportional to the concentration
of the organic cation. Very likely, the role of TMA in the formation
of nanocrystals is not a structural one but corresponds to a shift of
the balance between kinetics of nucleation and growth of the crys-
tals. The formation of nanocrystals of faujasite in the presence of a
limited amount of TMA can significantly improve the economical
attractiveness of these materials.
Acknowledgments
The authors acknowledge the technical support of Thomas
Cacciaguerra and Géraldine Layrac and the financial support of
theAlgerian Ministry for Higher Education and Research and of the
Tassili program 12MDU857 “Porous Materials for Environment and
Healthcare”.
References
[1] E.A. Swabb, B.C. Gates, Ind. Eng. Chem. Fundam. 11 (1972) 540–545.
[2] S. Al-Khattaf, H.I. de Lasa, Can. J. Chem. Eng. 79 (2001) 341–348.
[3] L. Tosheva, V.P. Valtchev, Chem. Mater. 17 (2005) 2494–2513.
[4] S.C. Larsen, J. Phys. Chem. C 111 (2007) 18464–18474.
[5] B.J. Schoeman, J. Sterte, J.E. Otterstedt, Zeolites 14 (1994) 110–116.
[6] N.B. Castagnola, P.K. Dutta, J. Phys. Chem. B 102 (1998) 1696–1702.
[7] G. Zhu, S. Qiu, J. Yu, Y. Sakamoto, F. Xiao, R. Xu, O. Terasaki, Chem. Mater. 10
(1998) 1483–1486.
[8] S. Mintova, V. Valtchev, Stud. Surf. Sci. Catal. 125 (1999) 141–148.
[9] B.A. Holmberg, Wang.F H., J.M. Norbeck, Y.N. Yan, Micropous Mesopous Mater.
59 (2003) 13–28.
[10] B.A. Holmberg, Wang.F H., Y.N. Yan, Micropous Mesopous Mater. 74 (2004)
189–198.
[11] V.R. Rani, R. Singh, P. Payra, P.K. Dutta, J. Phys. Chem. B 108 (2004) 20465–20470.
[12] H. Yin, T. Zhou, Y. Liu, Y. Chai, C. Liu, J. Porous Mater. 19 (2012) 277–281.
[13] C.H. Rüscher, N. Salman, J.C. Buhl, W. Lutz, Microporous Mesoporous Mater. 92
(2006) 309–311.
[14] O. Larlus, S. Mintova, T. Bein, Microporous Mesoporous Mater. 96 (2006)
405–412.
[15] T.F. Chaves, H.O. Pastore, D. Cardoso, Microporous Mesoporous Mater. 161
(2012) 67–75.
[16] F. Hamidi, A. Bengueddach, Z. Derriche, F. Fajula, F. Di Renzo, J. Soc. Chim. Tun.
3 (1993) 373–383.
[17] Y.C. Kim, J.Y. Jeong, J.Y. Hwang, S.D. Kim, W.J. Kim, J. Porous Mater. 16 (2009)
299–306.
[18] F. Di Renzo, Catal. Today 41 (1998) 37–40.
[19] S.P. Zhdanov, in: R.M. Barrer (Ed.), Molecular Sieves, Society of Chemical Indus-
try, London, 1968, pp. 62–70.
[20] M. Pamba, G. Maurin, S. Devautour, J. Vanderschueren, J.C. Giuntini, F. Di Renzo,
F. Hamidi, Phys. Chem. Chem. Phys. 2 (2000) 2027–2031.
[21] F.G. Dwyer, P. Chu, J. Catal. 59 (1979) 263–271.
[22] N. Bouchiba, M.L. Guzman Castillo, A. Bengueddach, F. Fajula, F. Di Renzo, Micro-
porous Mesoporous Mater. 144 (2011) 195–199.
[23] R.H. Jarman, M.T. Melchior, J. Chem. Soc. Chem. Commun. (1984) 414–416.
[24] B. Mihailova, M. Wagner, S. Mintova, T. Bein, Stud. Surf. Sci. Catal. 154 (2004)
163–170.
[25] G. Kühl, H. Robson, in: K.P. Lilletud (Ed.), Verified Syntheses of Zeolitic Materials,
Second Ed., Elsevier, Amsterdam, 2001, pp. 185–187.
[26] R.A. Rakoczy, Y. Traa, Microporous Mesoporous Mater. 60 (2003) 69–78.