Microporous and Mesoporous Materials 69 (2004) 35–42

www.elsevier.com/locate/micromeso

Electrophoretic deposition of nanosized zeolites

in non-aqueous medium and its application in fabricating
thin zeolite membranes
Wei Shan a, Yahong Zhang a, Wuli Yang b, Chen Ke a, Zi Gao a, Yunfen Ye a, Yi Tang a,*

a
Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University,
Shanghai 200433, PR China
b
Department of Macromolecular Science and Key Laboratory of Molecular Engineering of Polymers, Ministry of Education,
Fudan University, Shanghai 200433, PR China
Received 25 September 2003; received in revised form 21 January 2004; accepted 24 January 2004

Abstract

Thin zeolite films with thicknesses from several hundred nanometers to a few micrometers have been fabricated through elec-
trophoretic deposition (EPD) in acetylacetone (Acac) and/or isopropyl alcohol (IPA). Various types of nanosized zeolites with
different Si/Al ratios ranging from 1.6 (zeolite LTA) to nearly infinity (silicalite-1) were applied to prepare the EPD suspensions and
showed different behaviors in EPD. The EPD rate of zeolite particles in non-aqueous medium was much higher than that in aqueous
system mainly due to the high voltage applied, and consequently the whole process was usually completed in a few seconds. It was
found that the Al/(Si + Al) ratios of zeolites and the chemical/physical properties of the EPD medium were two crucial factors which
affected the thickness and density of the zeolite films prepared by EPD. The zeolite films fabricated through EPD could be effectively
densified by secondary growth to prepare compact zeolite membranes.

2004 Elsevier Inc. All rights reserved.

Keywords: Zeolite film/membrane; Electrophoretic deposition (EPD); Non-aqueous medium; Secondary growth; Nanosized zeolite

1. Introduction Practically, thin zeolite membranes or films, especially in

Zeolite membranes or films have been paid much
attention in recent years because of their uniform
micropore structure, good thermal stability, high
mechanical strength and resistance to relatively extreme
chemical environment [1–7]. Membranes that are com-
posed of different type of zeolites provide different
framework structure and pore size, which make them
suitable for the application in separating various small
molecules [6]. Moreover, the Si/Al ratios of zeolite
membranes determine their acidity and hydrophilicity/
hydrophobicity, and consequently their catalytic and
separating performance [1,3–5]. In the last few decades,
supported zeolite membranes or films have also been
adopted as zeolite-modified electrodes [8,9], which
mainly relied on the ion-exchange property of zeolites.
*
Corresponding author. Tel.: +86-21-55664125; fax: +86-21-
65641740.
E-mail address: yitang@fudan.edu.cn (Y. Tang).
submicrometer scale, might be more preferred in appli-
cations due to their high fluxes in separation or fast ion
transport rate in zeolite-modified electrode. Tavolaro
et al. [3] divided the available techniques along the
preparation process of zeolite membrane into four cat-
egories: (1) pre-treatment of the supports, (2) synthetic
methodology, (3) impregnation of the supports, and (4)
elimination of small defects. As the key technique, a
number of synthetic methods such as in situ synthesis
[10], layer-by-layer (LbL) assembly [11] and seed-film
method [12] have been successively developed. However,
there still existed some defects in most of the synthetic
methods. For example, in situ synthesis was a facile
method of fabricating zeolite membranes, but the mem-
brane thickness could not be precisely adjusted. On the
other hand, although LbL assembly of nanosized zeo-
lites with electrostatic attraction was considered as one
of the most effective ways to control the thickness of
zeolite layers, its operation was somewhat time-con-
suming. Therefore, a more facile and controllable

1387-1811/$ - see front matter
2004 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2004.01.003
36 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42
approach to fabricate zeolite membranes or films is still
needed.
Electrophoretic deposition (EPD) is a universal
method of coating substrates with a variety of charged
fine particles from colloidal suspension [13], and no
pretreatment of substrate is needed in most cases. By
this method, the guest particles with different composi-
tion and structure can homogeneously deposit on the
surface of a substrate to form a uniform coating or even
obtain a free-standing object which replicate the mor-
phology of the substrate after removing the substrate.
Takayama et al. [14] firstly introduced this technique to
prepare zeolite Na–A, Na–Y and H-ZSM-5 films in
acetonitrile, acetone and acetonitrile added benzoic acid,
respectively. Ahlers et al. fabricated zeolite-modified
electrodes by EPD of zeolite 13X, Y and 4A in
Et4 NClO4 /CH3 CN [15] and studied their voltammetric
behaviors [16]. Coupled with secondary growth, Seike
et al. [17,18] further prepared compact FAU-type zeolite
membrane and characterized its performance in sepa-
ration. Yu et al. [19] compared the traditional DC
voltage EPD and a pulsed voltage method. Except the
method of direct EPD of zeolite particles, Mohammadi
et al. [20] made a zeolite A membrane by EPD of pre-
cursor kaolin followed with hydrothermal crystalli-
zation. However, the thicknesses of the zeolite films
obtained in all of these works were in micrometer scale
and somewhat difficult to be precisely controlled be-
cause of the relatively large size of their building blocks,
i.e. micrometer-sized zeolite crystals or precursors. To
the best of our knowledge, the only reports concerning
the preparation of ultrathin zeolite film by EPD with
nanosized zeolites as building blocks were the work of
fabricating hollow silicalite-1 fibers by Ke et al. [21,22].
However, because the EPD process was carried out in
an aqueous system, the voltage was limited to below 3 V
to avoid the electrolysis of water, leading to a relatively
long EPD time (e.g. 2 · 10 min at 2 V).
In the present work, we systematically study the EPD
behavior of various-type nanosized zeolites in non-
aqueous mediums where a much higher voltage can be
Table 1
Synthesis of various-type nanosized zeolites
Zeolite type Chemical composition of gel
MFI (silicalite-1) 4.5(TPA)2 O:25SiO2 :480H2 O:100EtOH
MFI (ZSM-5) 4.5(TPA)2 O:0.25Al2 O3 :25SiO2 :
480H2 O:100EtOH
BEA 12(TEA)2 O:Al2 O3 :60SiO2 :588H2 O
SOD 14(TMA)2 O:0.85Na2 O:40SiO2 :
Al2 O3 :805H2 O
LTL 10K2 O:Al2 O3 :20SiO2 :400H2 O
LTA 2.46(TMA)2 O:0.43Na2 O:Al2 O3 :
3.40SiO2 :370H2 O:13.60EtOH
a
Templates TPAOH, TEAOH and TMAOH were aqueous solutions with concentration of 25 wt.%.
b
Colloidal silica: SiO2 40 wt.%, Al2 O3 0.103 wt.%.
applied by contrast with the aqueous system. Thin
zeolite films with thicknesses from several hundred na-
nometers to a few micrometers have been successfully
assembled on stainless steel grid substrates using zeolite
MFI (including silicalite-1 and ZSM-5), BEA, SOD,
LTL and LTA crystals as building blocks. To eliminate
the intercrystalline pores of the zeolite films prepared by
EPD, secondary growth by hydrothermal treatment was
surveyed for zeolite MFI and LTA films.
2. Experimental
2.1. Synthesis of nanosized zeolites
The zeolite particles applied as building blocks in
EPD were hydrothermally synthesized according to the
literature [23–28]. Detailed synthetic conditions and re-
agents are listed in Table 1. All of the reagents were
chemically or analytically pure and used without further
purification. The particle sizes and Si/Al ratios of zeolite
crystals were determined by scanning electron micro-
scope (SEM) and energy dispersive X-ray spectrometer
(EDS), respectively and listed in Table 2. According to
their X-ray diffraction (XRD) patterns and SEM ima-
ges, all of the samples were well-crystallized nanozeo-
lites. They could be well dispersed in pure water or
organic solvent as suspensoid for a long time so that
stirring which was usually applied in EPD with
micrometer-sized zeolites [19] was not needed in our
experiments.
2.2. Preparation of EPD suspensions
The as-synthesized zeolites were washed thoroughly
with deionized water through centrifugation and ultra-
sonically redispersion for at least five cycles to remove
the excess reactants and lower the pH of suspension to
about 8. Then the zeolite particles were centrifugated
and redispersed in isopropyl alcohol (IPA) for three
cycles to exchange the medium from water to IPA.
Reagents Temperature Crystallization
(C) time (h)
TPAOH,a TEOS, H2 O 80 72
TPAOH,a TEOS, Al foil, H2 O 80 72
TEAOH,a fumed silica, Al foil, H2 O 140 240
TMAOH,a NaOH, colloidal silica,b 100 72
Al foil, H2 O
KOH, fumed silica, Al foil, H2 O 175 24
TMAOH,a NaOH, TEOS, Al foil, 100 48
H2 O
 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42 37

Table 2 power supply. The platinum crucible was connected

Particle size and Si/Al ratio of synthesized zeolites with the other electrode (typically the cathode) of the
Zeolite type Particle size (nm) Si/Al power supply. After EPD, the stainless steel grid with
MFI(silicalite-1) 80–100 infinity zeolite coating was rinsed in IPA to remove the excess
MFI(ZSM-5) 150–200 43.7 suspension and dried at room temperature.
BEA 80–100 29.4
SOD 80–100 10.5
LTL 100 · 150a 2.9 2.4. Secondary growth of zeolite film fabricated by EPD
LTA 250–300 1.6
a
Zeolites LTL were rod-like crystals. After EPD of zeolite MFI (silicalite-1) and LTA in
the mixed medium of Acac and IPA (volume ratio ¼ 5:1)
When preparing the suspensions of zeolites in acetyl- at 200 V for 60 s, the resulting zeolite films on stainless
acetone (Acac), IPA was further removed by centri- steel grids were densified by hydrothermal treatment in
fugation and redispersion in Acac twice. It was not solutions containing silicon/aluminum source according
recommended to directly exchange the water in aqueous to the literature [29,30]. The reagents and conditions of
suspension of zeolites with Acac because some types of secondary growth are listed in Table 3. After secondary
zeolites would form flocculent aggregates, which are not growth, the supported zeolite membranes were rinsed in
easily redispersed by ultrasonication. All of the zeolite deionized water and dried at room temperature.
suspensions were adjusted to a concentration of about
15 mg ml
1 for the purpose of EPD. 2.5. Characterization

2.3. EPD of zeolites in non-aqueous medium
A homemade AC-to-DC convertor was used as the
adjustable DC power supply and the accurate value of
EPD voltage was measured with a voltameter in parallel
connection. A 30 ml platinum crucible was applied as
both the container of zeolite suspension and one elec-
trode in EPD while the stainless steel grid (Fig. 1) was
used as the other electrode in EPD and the support of
zeolite film. After being washed by ultrasonication in
deionized water and acetone, the stainless steel grid was
vertically inserted into the suspension of zeolites and
connected with one electrode (typically the anode) of the
The crystalline type of zeolites was characterized by
XRD on a Rigaku D/max-IIA diffractometer with Cu–
Ka radiation at 30 kV and 20 mA. SEM images were
recorded on a Philips XL30 scanning electron micro-
scope to determine the size of zeolite crystals and the
thickness/density of the zeolite films fabricated by EPD.
EDS equipped on SEM was applied to characterize the
Si/Al ratios of zeolites. Zeta potentials of zeolite parti-
cles were measured on a Coulter DELSA 440SX.
3. Results and discussion
3.1. Effect of zeolite type

Various types of zeolite films fabricated by EPD on

Fig. 1. SEM image of the stainless steel grid substrate.
stainless steel grids at 50 V for 15 s in Acac are displayed
in Fig. 2. All types of zeolite particles deposited on the
stainless steel grid only when the grid was connected
with the anode of power supply, indicating that all types
of zeolites carried negative charges in Acac. Further-
more, it was found that pure-silica zeolite MFI (silica-
lite-1) only formed a monolayer coating on the stainless
steel grid, while aluminum-containing zeolites, including
MFI (ZSM-5), BEA, SOD, LTL and LTA fabricated
multilayer coatings.

Table 3
Secondary growth of zeolite films fabricated by EPD
Zeolite type Chemical composition of gel Reagents Temperature (C) Time (h)
MFI 28Na2 O:1.5Al2 O3 :100SiO2 :4000H2 O NaOH, Al2 (SO4 )3 Æ 18H2 O, colloidal 180 10
silica,a H2 O
LTA 80Na2 O:1Al2 O3 :9SiO2 :5000H2 O NaOH, Al2 (SO4 )3 Æ 18H2 O, 80 5
Na2 SiO3 Æ 9H2 O, H2 O
a
Colloidal silica: SiO2 40 wt.%, Al2 O3 0.103 wt.%.
38 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42

Fig. 2. SEM images of various-type zeolite films fabricated by EPD at 50 V for 15 s: (a) MFI (silicalite-1); (b) MFI (ZSM-5); (c) BEA; (d) SOD; (e)
LTL; (f) LTA.

The EPD behaviors of zeolites are in correspondence Zeolite particles with higher AlO
4 content carry more
with their electrical properties which result from surface negative charges in their framework and possess a
silicon hydroxyl groups (BSiAOH) and aluminum– stronger ‘‘shielding effect’’.
oxygen tetrahedrons (AlO
4 ) [31,32]. Except silicalite-1 The AlO
4 content in a zeolitic framework can be
that contains only BSiAOH, other types of zeolites in quantified by the Al/(Si + Al) ratio, and Fig. 3 illustrates
our study possess both of the above charge sites. the relation between the thickness of zeolite film and Al/
BSiAOH can donate/accept a proton to carry a nega- (Si + Al) ratio of zeolites, which exhibits an interesting
tive/positive charge as long as zeolites are dispersed in a volcano-like curve with zeolite BEA as the peak. As
medium that is not completely proton-inert, while the shown in the literature [31], most types of zeolites carry
charges caused by AlO
4 rely on the polarization of negative charges at neutral pH, and the isoelectric point
zeolite particles with compensating cations in the electric
field. The charges from BSiAOH are usually weaker
compared to the negative charges from AlO
4 , if the
medium is not so ready to donate or accept protons as
strong acid or base. Therefore, during the EPD process,
the aluminum-containing zeolite particles may migrate
toward the anode and their migrating velocity increases
with their AlO
4 content. However, as pointed out in the
literature [13], the pre-deposited particle layer (i.e. zeo-
lite film in our study) would cause a sharp potential drop
ðDudep Þ near the electrode, which would prevent parti-
cles in suspension from continuously depositing onto the
electrode. This ‘‘shielding effect’’ might intensify with Fig. 3. Relation between the thickness of zeolite film and Al/(Si + Al)
the increase of charges carried by the deposited particles. ratio of zeolite.
 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42
(IEP) of zeolite particles normally shift toward a lower
pH with the increase of its Al/(Si + Al) ratio. Moreover,
the absolute value of charge at the same pH generally
increased with the Al/(Si + Al) ratio of zeolites. There-
fore, zeolite particles with higher Al/(Si + Al) ratio pos-
sess higher migrating velocity in the electric field, which
can explain why the zeolite film thickened with the
increase of Al/(Si + Al) ratio of zeolites from MFI
(silicalite-1) to BEA. However, if the Al/(Si + Al) ratio
further increased, e.g. zeolites LTL and LTA, the film
thickness did not increase but reduced. This phenome-
non may be attributed to the strong ‘‘shielding effect’’ of
the high-aluminum zeolite layer during the EPD process
in that the previously coated zeolite particles with large
quantity of negative charges would hinder the particles
in suspension from deposition. Besides the Al/(Si + Al)
ratio, the morphology and particle size of zeolites may
also influence the compactness of zeolite films. Particles
with small size and regular morphology tend to fabricate
dense films. It is indicated by Fig. 2 that the zeolite BEA
film was more compact than zeolite LTL and LTA films
because the latter possessed either irregular morphology
or large size.
3.2. Effect of EPD medium
The medium used in EPD is another crucial factor
that determines the EPD behavior of zeolite particles.
The ability of the medium to donate/accept protons
strongly influences the protonation state of the
BSiAOH on the surface of zeolites, which will affect the
charge of the zeolite crystals in suspension, and conse-
quently their electrophoretic mobility and depositing
efficiency, especially for pure-silica or high-silica zeo-
lites. Additionally, some physical properties of the
medium, such as dielectric constant, specific conductiv-
ity and viscosity index also affected the electrophoretic
mobility of particles in the electric field [15]. Two com-
monly used non-aqueous mediums in EPD, here, IPA
and Acac were applied to show the effect of medium on
the EPD behaviors of zeolites due to their different
mechanisms of donating/accepting protons, as illustra-
ted in Scheme 1. IPA normally behaved as a proton
donor in EPD owing to its hydroxyl group [33], while
Acac as ketone was a weak Br€ onsted base, which could
accept proton on its carbonyl oxygen [34]. Moreover,
the enol-form of Acac is more stable than its keto-form
in organic solvent due to the formation of an intra-
molecular 6-member ring structure with conjugated
double bond. Either of the two oxygen atoms can accept
a proton, whose positive charge can be easily dispersed
in the electron-sufficient conjugated double bond
through resonance (or delocalized p-bond according to
the molecular orbital theory).
Silicalite-1 was chosen to investigate the medium ef-
fect because its aluminum-free framework could exclude
39
Scheme 1. Mechanisms of the proton transfer between the silicon hy-
droxyl species on the surface of silicalite-1 particle and the non-
aqueous EPD mediums: BSiAO
accepts proton from IPA and
transforms to BSiAOH; BSiAOH donates proton to Acac and
transforms to BSiAO
.
the influence of AlO
4 . Fig. 4a and b show the SEM
images of silicalite-1 films obtained at a moderate con-
dition (100 V, 5 s) in IPA and Acac, respectively. It was
found that silicalite-1 could form only a dense mono-
layered coating (about 100 nm thick) in the former but
formed a zeolite film as thick as 7.1 lm in the latter.
When the EPD time was prolonged to 10 s at the same
voltage, the film prepared in Acac thickened to 20.3 lm
while that in IPA seemed to have no significant changes.
These phenomena can be attributed to the different
proton transfer mechanism between silicalite-1 and EPD
mediums. The silicon hydroxyl groups on the surface of
as-synthesized silicalite-1 are mostly in the form of
BSiAO
(TPAþ ), which can ionize to BSiAO
and
TPAþ . With the wash of the nanozeolite particles using
deionized water before exchanging non-aqueous med-
ium, BSiAO
(TPAþ ) gradually transforms to BSiAOH
with the lowering of both TPAþ concentration and pH
value of solution. As a result, BSiAOH and BSiAO

coexist on the surface of silicalite-1 particles in our
study. Acac possesses a certain ability to accept a proton
due to the electron-sufficient conjugated double bond
through resonance (or delocalized p-bond) in its enol-
form as described previously, so that protons would
further transfer from BSiAOH to Acac compared to the
aqueous system, which make zeolite particles in Acac
medium carry more negative charges and exhibit higher
electrophoretic mobility. On the contrary, IPA as a
proton donor would give protons to BSiAO
and
40 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42
Fig. 4. SEM images of zeolite films by EPD of nanosized silicalite-1 at 100 V for 5 s in (a) IPA and (b) Acac.
decrease the negative charges of zeolite particles, which
cause a lower EPD rate in IPA medium. The above
mechanisms could also be supported by the zeta po-
tential values of silicalite-1 in IPA, water (pH  8) and
Acac, which were )24.4, )50.0 and )76.1 mV, respec-
tively. Besides the chemical properties of medium, the
lower viscosity index, higher dielectric constant and
lower specific conductivity of Acac compared to IPA
also benefit the electrophoretic mobility of zeolite par-
ticles in Acac. To further confirm the proton transfer
mechanism, a mixed medium of Acac and IPA (volume
ratio ¼ 5:1) has also been applied to the EPD of silica-
lite-1. It is interesting that a monolayer coating was al-
ways obtained in all conditions we have attempted,
indicating that the transfer of protons from IPA to Acac
would prohibit that from zeolites to Acac because of the
competitive proton-donating effect of IPA.
3.3. Effect of EPD voltage/time and concentration of
suspension
Besides the properties of the zeolites and the effect of
medium, EPD voltage and time also influence the
thickness of zeolite film. To more clearly investigate the
effect of EPD voltage and time on the fabrication of
zeolite film, nanosized zeolite BEA with the highest EPD
rate in Acac was selected as an example. The thicknesses
of zeolite BEA films by EPD at 50, 100 and 150 V for 5 s
were 3.2, 6.5 and 10.4 lm, respectively. It is clear that
the film thickness increased with the EPD voltage for the
same EPD time, because particles would possess higher
electrophoretic mobility in more intensive electric field.
On the other hand, the thicknesses of zeolite BEA films
by EPD at 20 V for 5, 10, 20 and 30 s were 0.8, 1.8, 10.0
and 19.1 lm, respectively, indicating that the film
thickness could also be well controlled by changing the
EPD time. It can be expected that the film thickness will
be more easily controlled for other types of zeolites
whose EPD rates are lower than zeolite BEA.
The concentration of EPD suspension can affect the
film thickness and density by controlling the number of
particles depositing on the electrode in unit time. The
suspension of nanosized zeolite SOD (10 mg ml
1 ) was
diluted with Acac to one fifth of its initial concentration
and the thickness of the resulting film at 100 V for 5 s
reduced from 5.2 to 2.1 lm. Similarly, if the EPD time
was prolonged to 10 s at the same voltage, the film
thickness with high and low concentration of suspension
increased to 10.4 and 5.1 lm, respectively. Notably,
though thinner zeolite films seem to be easily obtained
through reducing the concentration of zeolite suspen-
sion than the adjustment of EPD voltage or time, the
compactness of zeolite film may be influenced accord-
ingly.
3.4. Secondary growth of zeolite film with hydrothermal
treatment
Although the zeolite particles assembled by EPD are
compactly arrayed, the nanoscale intercrystalline pores
between zeolite crystals will be fatal in some applications
such as separation of small molecules. Therefore, a post-
treatment process is sometimes necessary to prepare a
pinhole-free zeolite membrane. Takayama et al. [14]
developed a method called ‘‘non-sintering treatment’’ to
fill the intercrystalline pores with colloidal silica. How-
ever, this mending approach decreased the fraction of
zeolite in the membrane and lowered the quality of
zeolite membrane to some extent. Seike et al. [17,18]
obtained a dense zeolite membrane as thick as 60 lm by
secondary growth method, i.e., hydrothermally treating
the zeolite FAU membrane prepared by EPD in solu-
tions containing silicon/aluminum source. Based on the
latter work, we have successfully fabricated dense and
ultrathin zeolite membrane with controllable thickness
by secondary growth of the nanosized zeolite coating
pre-assembled by EPD method, which may provide a
high-performance zeolitic membrane material for the
application in the processes involving small molecules
because of its ultrathin and defect-free character.
Fig. 5a and b display the SEM images of the sub-
micrometer-scale zeolite membranes prepared by hydro-
thermally treating the monolayered coating of zeolite
MFI (silicalite-1) and LTA on the stainless steel grid,
showing that the intercrystalline pores disappeared with
the intergrowth of zeolite crystals. Zeolite membranes
 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42 41

Fig. 5. SEM images of zeolite membranes fabricated by secondary growth: (a) MFI (monolayered seeds, 10 h); (b) LTA (monolayered seeds, 5 h); (c)
MFI (after ultrasonication); (d) LTA (after ultrasonication); (e) MFI (monolayered seeds, 24 h); (f) MFI (multilayered seeds, 24 h).

densified by secondary growth exhibited high mechani-
cal strength and maintained their initial morphologies
after being ultrasonicated in an ultrasonic bath (50 kHz,
120 W) for 15 min, as shown in Fig. 5c and d. A 5.6-lm-
thick zeolite MFI membrane (Fig. 5e) was obtained if
the period of secondary growth was prolonged to 24 h.
It can be expected that the thickness of zeolite mem-
branes may be controlled from submicrometer to several
micrometers by the adjustment of secondary growth
period.
To further study the effect of zeolite seeds on the
resulting zeolite membrane by secondary growth, we
hydrothermally treated a multilayered zeolite MFI (sil-
icalite-1) coating with thickness of about 20 lm. It was
found that the growth of zeolite seeds only occurred
near the outer surface of the precursor film, leaving most
of the interior zeolite particles unchanged, as shown in
Fig. 5f. This phenomenon may be explained by the rel-
atively lower permeating velocity of silicon/aluminum
source compared to the growth rate of zeolite mem-
brane, i.e., the dense and rapidly formed zeolite mem-
brane on the outer surface of zeolite coating induced by
the zeolite seeds prevented the inner zeolite particles
from contacting the silicon/aluminum source in the
solution. It is also clear from Fig. 5e and f that the
crystal size of zeolite MFI membrane densified from a
multilayer of nanosized zeolite is much smaller than that
prepared from monolayer because of the larger number
of seeds during secondary growth in the former condi-
tion.
4. Conclusions
Various types of zeolite films with controllable
thickness have been fabricated with high speed through
EPD in non-aqueous medium. Different types of zeolites
showed different EPD behaviors due to their individual
Al/(Si + Al) ratio. The EPD of zeolites is more efficient
in Acac than in IPA because of their different chemical
and physical properties. EPD voltage/time and concen-
tration of suspension, which were normally applied in
EPD to control the resulting coating, can also be used in
the EPD of zeolites to adjust the film thickness.
Hydrothermal treatment of a zeolite-seeded stainless
steel grid by EPD resulted in dense and ultrathin zeolite
42 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42
MFI and LTA membranes with high mechanical
strength, which is advantageous for their practical
applications. Although only stainless steel grid was used
as substrate in our study, this method may be extended
to other removable substrates such as carbon fibers to
fabricate self-supporting ultrathin zeolite membranes.
Acknowledgements
The authors thank H.Y. Chen for her help in the
SEM characterization. This work is supported by the
NSFC (20273016, 20233030, 20303003, 20325313) and
the SNPC (0249nm028, 03DJ14004).
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