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Electrophoretic Deposition of Nanosized Zeolites in Non-Aqueous Medium and Its Application in Fabricating Thin Zeolite Membranes
Electrophoretic Deposition of Nanosized Zeolites in Non-Aqueous Medium and Its Application in Fabricating Thin Zeolite Membranes
Electrophoretic Deposition of Nanosized Zeolites in Non-Aqueous Medium and Its Application in Fabricating Thin Zeolite Membranes
www.elsevier.com/locate/micromeso
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
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 applied by contrast with the aqueous system. Thin
needed. zeolite films with thicknesses from several hundred na-
Electrophoretic deposition (EPD) is a universal nometers to a few micrometers have been successfully
method of coating substrates with a variety of charged assembled on stainless steel grid substrates using zeolite
fine particles from colloidal suspension [13], and no MFI (including silicalite-1 and ZSM-5), BEA, SOD,
pretreatment of substrate is needed in most cases. By LTL and LTA crystals as building blocks. To eliminate
this method, the guest particles with different composi- the intercrystalline pores of the zeolite films prepared by
tion and structure can homogeneously deposit on the EPD, secondary growth by hydrothermal treatment was
surface of a substrate to form a uniform coating or even surveyed for zeolite MFI and LTA films.
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 2. Experimental
prepare zeolite Na–A, Na–Y and H-ZSM-5 films in
acetonitrile, acetone and acetonitrile added benzoic acid, 2.1. Synthesis of nanosized zeolites
respectively. Ahlers et al. fabricated zeolite-modified
electrodes by EPD of zeolite 13X, Y and 4A in The zeolite particles applied as building blocks in
Et4 NClO4 /CH3 CN [15] and studied their voltammetric EPD were hydrothermally synthesized according to the
behaviors [16]. Coupled with secondary growth, Seike literature [23–28]. Detailed synthetic conditions and re-
et al. [17,18] further prepared compact FAU-type zeolite agents are listed in Table 1. All of the reagents were
membrane and characterized its performance in sepa- chemically or analytically pure and used without further
ration. Yu et al. [19] compared the traditional DC purification. The particle sizes and Si/Al ratios of zeolite
voltage EPD and a pulsed voltage method. Except the crystals were determined by scanning electron micro-
method of direct EPD of zeolite particles, Mohammadi scope (SEM) and energy dispersive X-ray spectrometer
et al. [20] made a zeolite A membrane by EPD of pre- (EDS), respectively and listed in Table 2. According to
cursor kaolin followed with hydrothermal crystalli- their X-ray diffraction (XRD) patterns and SEM ima-
zation. However, the thicknesses of the zeolite films ges, all of the samples were well-crystallized nanozeo-
obtained in all of these works were in micrometer scale lites. They could be well dispersed in pure water or
and somewhat difficult to be precisely controlled be- organic solvent as suspensoid for a long time so that
cause of the relatively large size of their building blocks, stirring which was usually applied in EPD with
i.e. micrometer-sized zeolite crystals or precursors. To micrometer-sized zeolites [19] was not needed in our
the best of our knowledge, the only reports concerning experiments.
the preparation of ultrathin zeolite film by EPD with
nanosized zeolites as building blocks were the work of 2.2. Preparation of EPD suspensions
fabricating hollow silicalite-1 fibers by Ke et al. [21,22].
However, because the EPD process was carried out in The as-synthesized zeolites were washed thoroughly
an aqueous system, the voltage was limited to below 3 V with deionized water through centrifugation and ultra-
to avoid the electrolysis of water, leading to a relatively sonically redispersion for at least five cycles to remove
long EPD time (e.g. 2 · 10 min at 2 V). the excess reactants and lower the pH of suspension to
In the present work, we systematically study the EPD about 8. Then the zeolite particles were centrifugated
behavior of various-type nanosized zeolites in non- and redispersed in isopropyl alcohol (IPA) for three
aqueous mediums where a much higher voltage can be cycles to exchange the medium from water to IPA.
Table 1
Synthesis of various-type nanosized zeolites
Zeolite type Chemical composition of gel Reagents Temperature Crystallization
(C) time (h)
MFI (silicalite-1) 4.5(TPA)2 O:25SiO2 :480H2 O:100EtOH TPAOH,a TEOS, H2 O 80 72
MFI (ZSM-5) 4.5(TPA)2 O:0.25Al2 O3 :25SiO2 : TPAOH,a TEOS, Al foil, H2 O 80 72
480H2 O:100EtOH
BEA 12(TEA)2 O:Al2 O3 :60SiO2 :588H2 O TEAOH,a fumed silica, Al foil, H2 O 140 240
SOD 14(TMA)2 O:0.85Na2 O:40SiO2 : TMAOH,a NaOH, colloidal silica,b 100 72
Al2 O3 :805H2 O Al foil, H2 O
LTL 10K2 O:Al2 O3 :20SiO2 :400H2 O KOH, fumed silica, Al foil, H2 O 175 24
LTA 2.46(TMA)2 O:0.43Na2 O:Al2 O3 : TMAOH,a NaOH, TEOS, Al foil, 100 48
3.40SiO2 :370H2 O:13.60EtOH H2 O
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.%.
W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42 37
2.3. EPD of zeolites in non-aqueous medium The crystalline type of zeolites was characterized by
XRD on a Rigaku D/max-IIA diffractometer with Cu–
A homemade AC-to-DC convertor was used as the Ka radiation at 30 kV and 20 mA. SEM images were
adjustable DC power supply and the accurate value of recorded on a Philips XL30 scanning electron micro-
EPD voltage was measured with a voltameter in parallel scope to determine the size of zeolite crystals and the
connection. A 30 ml platinum crucible was applied as thickness/density of the zeolite films fabricated by EPD.
both the container of zeolite suspension and one elec- EDS equipped on SEM was applied to characterize the
trode in EPD while the stainless steel grid (Fig. 1) was Si/Al ratios of zeolites. Zeta potentials of zeolite parti-
used as the other electrode in EPD and the support of cles were measured on a Coulter DELSA 440SX.
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 3. Results and discussion
connected with one electrode (typically the anode) of the
3.1. Effect of zeolite type
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 39
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 diluted with Acac to one fifth of its initial concentration
cause a lower EPD rate in IPA medium. The above and the thickness of the resulting film at 100 V for 5 s
mechanisms could also be supported by the zeta po- reduced from 5.2 to 2.1 lm. Similarly, if the EPD time
tential values of silicalite-1 in IPA, water (pH 8) and was prolonged to 10 s at the same voltage, the film
Acac, which were )24.4, )50.0 and )76.1 mV, respec- thickness with high and low concentration of suspension
tively. Besides the chemical properties of medium, the increased to 10.4 and 5.1 lm, respectively. Notably,
lower viscosity index, higher dielectric constant and though thinner zeolite films seem to be easily obtained
lower specific conductivity of Acac compared to IPA through reducing the concentration of zeolite suspen-
also benefit the electrophoretic mobility of zeolite par- sion than the adjustment of EPD voltage or time, the
ticles in Acac. To further confirm the proton transfer compactness of zeolite film may be influenced accord-
mechanism, a mixed medium of Acac and IPA (volume ingly.
ratio ¼ 5:1) has also been applied to the EPD of silica-
lite-1. It is interesting that a monolayer coating was al- 3.4. Secondary growth of zeolite film with hydrothermal
ways obtained in all conditions we have attempted, treatment
indicating that the transfer of protons from IPA to Acac
would prohibit that from zeolites to Acac because of the Although the zeolite particles assembled by EPD are
competitive proton-donating effect of IPA. compactly arrayed, the nanoscale intercrystalline pores
between zeolite crystals will be fatal in some applications
3.3. Effect of EPD voltage/time and concentration of such as separation of small molecules. Therefore, a post-
suspension treatment process is sometimes necessary to prepare a
pinhole-free zeolite membrane. Takayama et al. [14]
Besides the properties of the zeolites and the effect of developed a method called ‘‘non-sintering treatment’’ to
medium, EPD voltage and time also influence the fill the intercrystalline pores with colloidal silica. How-
thickness of zeolite film. To more clearly investigate the ever, this mending approach decreased the fraction of
effect of EPD voltage and time on the fabrication of zeolite in the membrane and lowered the quality of
zeolite film, nanosized zeolite BEA with the highest EPD zeolite membrane to some extent. Seike et al. [17,18]
rate in Acac was selected as an example. The thicknesses obtained a dense zeolite membrane as thick as 60 lm by
of zeolite BEA films by EPD at 50, 100 and 150 V for 5 s secondary growth method, i.e., hydrothermally treating
were 3.2, 6.5 and 10.4 lm, respectively. It is clear that the zeolite FAU membrane prepared by EPD in solu-
the film thickness increased with the EPD voltage for the tions containing silicon/aluminum source. Based on the
same EPD time, because particles would possess higher latter work, we have successfully fabricated dense and
electrophoretic mobility in more intensive electric field. ultrathin zeolite membrane with controllable thickness
On the other hand, the thicknesses of zeolite BEA films by secondary growth of the nanosized zeolite coating
by EPD at 20 V for 5, 10, 20 and 30 s were 0.8, 1.8, 10.0 pre-assembled by EPD method, which may provide a
and 19.1 lm, respectively, indicating that the film high-performance zeolitic membrane material for the
thickness could also be well controlled by changing the application in the processes involving small molecules
EPD time. It can be expected that the film thickness will because of its ultrathin and defect-free character.
be more easily controlled for other types of zeolites Fig. 5a and b display the SEM images of the sub-
whose EPD rates are lower than zeolite BEA. micrometer-scale zeolite membranes prepared by hydro-
The concentration of EPD suspension can affect the thermally treating the monolayered coating of zeolite
film thickness and density by controlling the number of MFI (silicalite-1) and LTA on the stainless steel grid,
particles depositing on the electrode in unit time. The showing that the intercrystalline pores disappeared with
suspension of nanosized zeolite SOD (10 mg ml1 ) was 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- from contacting the silicon/aluminum source in the
cal strength and maintained their initial morphologies solution. It is also clear from Fig. 5e and f that the
after being ultrasonicated in an ultrasonic bath (50 kHz, crystal size of zeolite MFI membrane densified from a
120 W) for 15 min, as shown in Fig. 5c and d. A 5.6-lm- multilayer of nanosized zeolite is much smaller than that
thick zeolite MFI membrane (Fig. 5e) was obtained if prepared from monolayer because of the larger number
the period of secondary growth was prolonged to 24 h. of seeds during secondary growth in the former condi-
It can be expected that the thickness of zeolite mem- tion.
branes may be controlled from submicrometer to several
micrometers by the adjustment of secondary growth
period. 4. Conclusions
To further study the effect of zeolite seeds on the
resulting zeolite membrane by secondary growth, we Various types of zeolite films with controllable
hydrothermally treated a multilayered zeolite MFI (sil- thickness have been fabricated with high speed through
icalite-1) coating with thickness of about 20 lm. It was EPD in non-aqueous medium. Different types of zeolites
found that the growth of zeolite seeds only occurred showed different EPD behaviors due to their individual
near the outer surface of the precursor film, leaving most Al/(Si + Al) ratio. The EPD of zeolites is more efficient
of the interior zeolite particles unchanged, as shown in in Acac than in IPA because of their different chemical
Fig. 5f. This phenomenon may be explained by the rel- and physical properties. EPD voltage/time and concen-
atively lower permeating velocity of silicon/aluminum tration of suspension, which were normally applied in
source compared to the growth rate of zeolite mem- EPD to control the resulting coating, can also be used in
brane, i.e., the dense and rapidly formed zeolite mem- the EPD of zeolites to adjust the film thickness.
brane on the outer surface of zeolite coating induced by Hydrothermal treatment of a zeolite-seeded stainless
the zeolite seeds prevented the inner zeolite particles steel grid by EPD resulted in dense and ultrathin zeolite
42 W. Shan et al. / Microporous and Mesoporous Materials 69 (2004) 35–42
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