Journal of Membrane Science 544 (2017) 342–350

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Journal of Membrane Science

journal homepage: www.elsevier.com/locate/memsci

Synthesis of stable UiO-66 membranes for pervaporation separation of MARK

methanol/methyl tert-butyl ether mixtures by secondary growth
⁎
Feichao Wua, Lu Lina, Haiou Liua, Huanting Wangb, Jieshan Qiua, Xiongfu Zhanga,
a
State Key Laboratory of Fine Chemicals, School of Chemical Engineering, Dalian University of Technology, Dalian 116024, China
b
Department of Chemical Engineering, Monash University, Clayton, Victoria 3800, Australia

A R T I C L E I N F O A B S T R A C T

Keywords: Stable UiO-66 membranes were successfully prepared on macroporous alumina tubes by secondary growth and
Metal-organic framework membrane were for the first time applied in the separation of methanol/methyl tert-butyl ether (MTBE) mixtures by per-
Membrane separation vaporation. Two key factors affecting the growth of the UiO-66 membranes were investigated. It has been found
Liquid separation that acetic acid promotes the crystallization of UiO-66 crystals and water favors the intergrowth of UiO-66
Pervaporation
crystals, leading to the formation of high-performance UiO-66 membranes. Under the optimized synthesis
conditions, a continuous and dense UiO-66 membrane could be obtained, showing a separation factor of nearly
600 and a flux of 1.21 kg m−2 h−1 for 5 wt% methanol/MTBE mixtures at 40 °C. The effects of operation
parameters on PV performance of the UiO-66 membranes were also studied in detail. The results reveal that
increasing feed temperature or methanol in feed would enhance permeation flux but reduce separation factor,
the permeability of components and membrane selectivity. It is worth mentioning that the UiO-66 membranes
show excellent operating stability. This work demonstrates that the UiO-66 membranes have great potential for
separation of methanol/MTBE mixtures via pervaporation.

1. Introduction
Due to environmental considerations, methyl tert-butyl ether
(MTBE) is generally used as an octane enhancer for gasoline to replace
the lead compounds. The MTBE industrial production process involves
the reaction of methanol with isobutylene, in which excessive methanol
is added to improve the conversion rate of isobutylene. However, as
methanol and MTBE can form an azeotrope mixture consisting of
14.3 wt% methanol at atmospheric pressure and 51 °C [1], conven-
tional separation process is usually achieved by addition of water, fol-
lowed by distillation to recycle the remaining methanol to the reactors
[2]. Obviously, this process is both expensive and energy intensive.
Pervaporation (PV), one typical membrane-based separation tech-
nology, is a promising alternative or supplement for the separation of
methanol/MTBE mixtures. Compared with traditional separation pro-
cesses, PV processes inherent advantages such as energy-saving, mod-
ularity and easy scale-up, the ability to separate heat-sensitive com-
ponents and the lack of theoretical limitation in the final product purity
[3]
To date, huge efforts have been devoted to designing membrane
materials for the separation of methanol/MTBE mixtures by perva-
poration, mostly polymeric membranes, covering cellulose acetate (CA)
[4–8], poly (vinyl alcohol) (PVA) [9–14], chitosan (CS) [15], cellulose
triacetate (CTA) [16], acrylic acid (AA) [17], polypyrrole (PPY) [18],
etc. Until now there exists only one commercially available polymeric
membrane (PERVAP 2256) for the separation of methanol/MTBE
mixtures [19]. The separation factor reduced from 180 to 25 and the
fluxes ranged from 0.68 to 1.35 kg m−2 h−1, when methanol in the feed
ranging from 10 to 30 wt%. Moreover, inorganic membranes such as
zeolites membranes have also been explored for extraction of methanol
from methanol/MTBE mixtures [20–22]. Although great progress has
been made, most membranes show obvious trade-off behavior in per-
vaporation. Therefore, it is desirable to search for novel membranes for
the separation of methanol/MTBE mixtures.
Metal-organic frameworks (MOFs) are novel hybrid in-
organic–organic materials that consist of metal ions or clusters bridged
by organic linkers [23,24] and possess ultra-high porosity, exceptional
high surface areas, flexibility in structure designing and diversity [25].
Thus they are excellent membrane candidates for application in gas or
liquid separation. In recent years, many impressive advances in the
fabrication of MOF-based gas separation membranes have been made
[26–30]. However, there have been few reports so far on MOF mem-
branes for separation of liquid mixtures, especially organic solvents,
since most MOF materials suffer from insufficient chemical or thermal

⁎
Corresponding author.
E-mail address: xfzhang@dlut.edu.cn (X. Zhang).

http://dx.doi.org/10.1016/j.memsci.2017.09.047
Received 26 June 2017; Received in revised form 9 September 2017; Accepted 12 September 2017
Available online 13 September 2017
0376-7388/ © 2017 Elsevier B.V. All rights reserved.
F. Wu et al.
stability in harsh environment. In addition, fabricating continuous MOF
membranes on porous substrates, especially tubular supports, is also
challenging because the preparation of some MOF membranes on a
porous tube is extremely difficult.
Very recently, Zirconium(IV)-carboxylate MOFs (Zr-MOFs) have
attracted much attention due to their high chemical and thermal sta-
bility. UiO-66 (UiO stands for University of Oslo), a typical Zr-based
MOF, was first reported by Cavka et al. [31]. The framework is built up
from Zr6O4(OH)4(CO2)12 clusters linked with 1,4-benzenedicarboxylate
(H2BDC) and has a main pore diameter of 6 Å [31,32]. This MOF shows
excellent thermal stability (up to 500 °C) owing to the presence of the
Zr6O4(OH)4 inorganic building blocks and remains unaltered towards a
number of organic solvents [33,34]. Accordingly, UiO-66 membranes
are expected to demonstrate its prosperous use in liquid separation. Yet,
as far as we know, UiO-66 membranes are more difficult to be prepared
than others, such as Zn-based ZIF membranes, thus there have been few
reports on continuous UiO-66 polycrystalline membranes [35–38]. Liu
et al. prepared well inter-grown UiO-66 membranes on alumina hollow
fibers for desalination and PV dehydration by an in-situ growth method
[35,36]. Friebe et al. [37] fabricated an oriented UiO-66 membrane on
ceramic α-Al2O3 support for gas separation, employing the secondary
growth method. Besides, Miyamoto et al. [38] reported an organo-se-
lective UiO-66 membrane synthesized by an in situ solvothermal
method. Therefore, UiO-66 membranes have demonstrated excellent
stability and have broad prospects in the field of separations, particu-
larly liquid separations. But it is still challenging for preparing defect-
free UiO-66 membranes due to the strict requirements on the growth of
UiO-66 membranes. Moreover, there is no report on UiO-66 membranes
for the separation of methanol/MTBE mixtures.
In the present work, a continuous and defect-free UiO-66 membrane
was fabricated on a macroporous tubular α-alumina support using the
secondary growth method and for the first time applied in the PV se-
paration of methanol/MTBE mixtures. UiO-66 nanocrystals were in-
troduced on the inner surface of the porous tube and employed as seeds
to induce the uniform growth of UiO-66 and thus form a compact
membrane. Furthermore, during the synthesis, both water and acetic
acid as two key factors were added to the synthesis solution to in-
vestigate the influences of their concentration in the synthesis solution
on the growth of UiO-66 membranes. Methanol/MTBE mixtures were
used to evaluate the achieved UiO-66 membranes, and the effect of
operation parameters on the PV performance were investigated in de-
tail. The resulting membranes presented high flux and separation factor
for methanol/MTBE mixtures. Specially, the UiO-66 membranes pre-
pared exhibited excellent stabilities in the methanol/MTBE mixtures,
even after long time tests, demonstrating a great potential in the
practical applications for PV separation of methanol/MTBE mixtures.
This work also further promotes the research progress for the pre-
paration of UiO-66 series membranes and opens up a novel application
for MOF membranes.
2. Experimental
2.1. Materials
The α-Al2O3 tubular supports (OD 10 mm, ID 8 mm and length
60 mm) were supplied by Fo Shan Ceramics Research Institute in this
study. The supports have a mean pore diameter of 0.2 µm. The zirco-
nium tetrachloride (ZrCl4, 99.5%) was provided by Alfa Aesar.
Terephthalic acid (99%), acetic acid (99.5%), N, N-Dimethyl for-
mamide (DMF, 99.5%), methanol (99.5%), methyl tert-butyl ether
(MTBE, 99.5%) were purchased from Sinopharm Chemical Reagent Co
(China). All chemicals above were used as received without further
purification. The deionized water and liquid nitrogen were home-made.
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Journal of Membrane Science 544 (2017) 342–350
2.2. Preparation of UiO-66 seeds and seed layers
UiO-66 seeds were prepared from a clear synthesis solution con-
taining 1 ZrCl4/1H2BDC/160 CH3COOH/320 DMF according to the
reports by Lu et al. [39]. ZrCl4 was dissolved in DMF by sonication for
5 min. H2BDC was added to the resulting solution and sonicated addi-
tional 5 min. After that, acetic acid was added to the solution. The re-
sulting mixture was stirred for 30 min, and then sealed into a Teflon-
lined autoclave, which was placed in the oven preheated to 120 °C for
24 h. The product was collected by centrifugation, washed three times
with DMF, and soaked in methanol for three days to exchange DMF.
Finally, the product was washed three times with methanol and dried
under vacuum.
The UiO-66 seed suspension was obtained by dispersing the above
obtained seeds into DMF solution through ultrasonic treatment. A thin
UiO-66 seed layer could be achieved on inner side of the support using
the dip-coating seeding method [40]. The seeding process was as fol-
lows: 1) the support wrapped with PTFE tape on outer surface were
dipped into the DMF suspension containing 1.0 wt% UiO-66 seeds for
10 s and dried for 3 h at 120 °C; 2) The dried support was rubbed with
degreasing cotton to remove superfluous seeds until there were no loose
seeds attached on the support surface; 3) the erased supports were
dipped into seed suspensions again for 2–3 s and dried. What's more, it
was necessary to improve adhesion of the UiO-66 seeds to the support
before secondary solvothermal growth by treating the seeded supports
at a higher temperature (200 °C).
2.3. Preparation of UiO-66 membranes
The precursor solutions for membrane growth were prepared by
mixing ZrCl4, H2BDC, H2O, CH3COOH and DMF to give a molar com-
position of ZrCl4/H2BDC/H2O/CH3COOH/DMF = 1:1:1:150:500. ZrCl4
was suspended in a half of the DMF, followed by adding acetic acid to
the solution and the mixture was sonicated with ultrasound for 10 min.
After that, H2BDC was dissolved in the remaining DMF and the re-
sulting solution was poured into the ZrCl4 solution. Water was added at
last and the final mixture was stirred at room temperature for 30 min.
Thereafter, the clear homogenous solution was transferred into a Teflon
lined stainless-steel autoclave in which the seeded support was placed
vertically trapped with PTFE tape on outer surface. The synthesis was
carried out in a convective oven at 120 °C for 72 h. To investigate the
influence of water and acetic acid, different amounts were used in the
membrane preparation. After crystallization, the as-synthesized mem-
branes were washed several times with DMF and ethanol. Then the
membranes were dried overnight at 25 °C under vacuum.
2.4. Characterization of UiO-66 membranes
The crystal structures of the synthesized seeds and membranes were
measured by x-ray diffraction (XRD) on a D/max-2400X-ray dif-
fractometer using Cu Ka radiation in the range of 5–40° at a scanning
rate of 8°/min. Field emission scanning electron microscopy (FE-SEM)
images of the as-synthesized seeds and seed layer were investigated by
the NOVA Nano SEM 450 (FEI Company). Scanning electron micro-
scopy (SEM) images of the UiO-66 membranes were obtained with a
QUANTA 450 (FEI Company) at an acceleration voltage of 30 kV after
gold coating. The zirconium distribution in the membrane was identi-
fied by energy dispersive X-ray (EDX) using the same QUANTA 450
equipped with an X-MAX 20 mm2/50 mm2.
The surface hydrophobic/hydrophilic properties of the UiO-66
membranes were measured on a contact angle instrument (OCAH200,
Data physics, Germany). Methanol and MTBE adsorption isotherms
were measured on UiO-66 powders collected from the bottom of the
autoclaves at 25 °C with a high vacuum electronic balance system
(Cahn-2000). To examine quality, the single gas permeation properties
of the UiO-66 membranes were evaluated using H2, N2 and CH4 in a
F. Wu et al.
home-made apparatus similar to our previous report [41].
The PV separation performance of the prepared UiO-66 membranes
for methanol/MTBE mixtures were evaluated at 40 °C employing a
homemade experimental device as shown in Fig. S1 in the Supporting
information. Total permeation flux was measured by weighing the
condensed vapor in a cold trap. Feed and permeate compositions were
determined through a gas chromatograph (GC 7890). The total per-
meation flux (J, kg m−2 h−1) and separation factor of methanol (αA / B )
were defined as:
Q
J=
At (1)
Yi / Yj
αi / j =
Xi / Xj (2)
where Q is the total weight (kg) of the permeate, A is the effective
membrane area (m2), t is the operation time (h) and Yi, Yj, Xi, Xj are
mass fractions of methanol and MTBE in the permeate and feed, re-
spectively.
To demonstrate the intrinsic properties of the UiO-66 membrane,
the membrane permeability Pi and membrane selectivity (β) were cal-
culated, as noted in the literature [42].
ji × l ji × l
Pi = = UiO-66 membrane.
Pio − pil γio χio piosat − pil (3)
Pi
β=
Pj (4)
where ji is the molar flux of component i, l is the thickness of the
membranes, Pio and Pil are the partial pressure of component i on the
feed side and the permeate side. γio and χio the activity coefficient and
mole fraction in feed, and Piosat is the saturated vapor pressure of the
pure component i. The relation calculations were completed with the
aid of Aspen Plus 8.4 software. Pi and Pj are the permeabilities of
component i and j.
3. Results and discussion
3.1. Synthesis of UiO-66 membrane by the secondary growth
To characterize the prepared UiO-66 seeds and UiO-66 membranes,
scanning electron microscope (SEM) and X-ray diffraction (XRD) were
conducted as shown in Fig. 1. The sharp peaks in the XRD patterns
indicate the excellent crystallinity of the seeds, and all the diffraction
peaks are consistent with the XRD pattern of standard UiO-66 free from
other crystalline phases, making it clear that the prepared seeds are
pure UiO-66 (see Fig. 1h). The SEM image in Fig. 1a shows that the
UiO-66 seeds synthesized in this study display uniform sizes of
100–200 nm, which can serve as seeds on the support for preparing
UiO-66 membranes. Generally, in-situ synthesis is a simple method for
fabricating crystalline membranes such as zeolites, MOFs, etc. How-
ever, it is very difficult to grow MOF membranes by the in-situ growth
because the heterogeneous nucleation and growth of MOF crystals on
the coarse macroporous tubular substrate is extremely unfavorable
[43]. As shown in Fig. 1d and e, indeed, the membrane obtained using
in-situ growth is discontinuous with visible holes or large boundary
voids. By contrast, seeded synthesis can decouple nucleation and
growth steps, modify some large voids of the macoporous tube and thus
offer better control over membrane microstructure [44]. Therefore, a
secondary growth approach was employed to prepare continuous UiO-
66 membranes.
As is shown in Fig. 1b and c, a very thin UiO-66 seed layer (1–2 µm)
is formed on the substrate surface after seeding, which is also confirmed
by the weak XRD pattern (Fig. 1h). The UiO-66 seed layer acts as both
the seeds for membrane growth and fillers to smooth the support and
reduce its large defects, favoring forming a perfect membrane. In
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Journal of Membrane Science 544 (2017) 342–350
comparison with the membrane from the in-situ growth, it is clearly
seen that the membrane surface from the secondary growth is well
inter-grown, free from any visible cracks or pinholes, and thus smoother
and more compact due to the existence of seed layer (see Fig. 1f), and
from the cross section view, the as-prepared membrane is uniform and
the thickness is about 6–7 µm (Fig. 1g). XRD results (Fig. 1h) confirm
that the membrane is typically pure crystalline UiO-66 phase structure,
which is in agreement with the previous report [35]. The EDX image
shows a sharp transition between the UiO-66 membrane layer (Zr
signal, green zone) and alumina substrate (Al signal, red zone) (see
Fig. 1i), revealing that the successful growth of a continuous UiO-66
layer on the support. What's more, UiO-66 powders collected from the
bottom of the autoclave (Fig. S2 in the Supporting information) are
octahedral in shape, which is in agreement with the grains in the
membrane.
3.2. Effect of two key factors on the growth of UiO-66 membrane
3.2.1. Effect of water
It was reported that the amount of water in the synthesis precursor
solution is vital to the formation of UiO-66 membranes [35,45]. Our
preliminary experimental results are exactly consistent with the report.
But there is no detailed study on the effect of water on the growth of
In order to thoroughly understand the role of water in UiO-66
membrane synthesis, a series of mother solutions with different H2O/
DMF molar ratios were prepared to investigate the influence of water
on the formation of UiO-66 membranes. Fig. 2 presents the SEM images
and XRD patterns of these membranes. When solvothermal synthesis
was carried out with no water, the seed layer is replaced by mono-
disperse octahedral crystals without intergrowth of UiO-66 crystals
(Fig. 2a and b), and this result is consistent with the weak diffractions in
Fig. 2k. In the case of 1:750, an amorphous layer appears on the support
(Fig. 2c and d) and characteristic peaks of UiO-66 are still weak. Then,
this amorphous phase is replaced by a thin UiO-66 sheet as long as the
H2O/DMF molar ratio in the mother solution increases to 1:550 (Fig. 2e
and f). As viewed from the top (Fig. 2e), the crystals on the surface
display octahedral in shape. Furthermore, the membrane thickness is
very thin (Fig. 2f), which is similar to that of the seed layer. However,
some defects or holes can be found on membrane surface and crystal-
linity of the membrane remains low. From this point onwards, with
increasing the amount of water, the UiO-66 layer begins to become
thicker and the grain sizes become bigger at the same time. Finally, a
continuous UiO-66 membrane layer forms when the mole ratio of water
to ZrCl4 in mother solution is exactly equal. As is shown in Fig. 2g, the
membrane surface is smoother and more compact compared with pre-
vious membranes. The SEM cross-sectional view (Fig. 2h) shows that
the UiO-66 membrane is 6–7 µm in thickness. XRD patterns confirm
pure crystalline phase of the membrane. Nevertheless, a little bit of
excess water would leads to the failure of the formation of high-quality
UiO-66 membranes. Just as the case of 1:450 (Fig. 2i and j), the shapes
of crystals become fuzzy accompanied by obvious decrease in X-ray
diffraction intensities.
Based on the above facts, it comes to the conclusion that water is
extremely important in UiO-66 membrane synthesis. On one hand,
water can enhance nucleation of UiO-66 crystals by promoting the
hydrolysis of the Zirconium precursor [46,47]. In fact, this is very im-
portant for membrane growth because fast nucleation rate can avoid
seeds peeling off from the substrate for the seeded synthesis [48] and
favor growing a continuous membrane. On the other hand, water can
supply oxygen atoms to the Zr6O4(OH)4(O2C)12 SBU, directly enhan-
cing the formation of the SBU [47]. Hence water can promote the in-
tergrowth of UiO-66 particles during the membrane growth, which is
closely related with membrane quality. In the synthesis of UiO-66
powder, the addition of water only affects the formation rates and the
sizes of the UiO-66 crystals. Nevertheless, the story is quite different in
F. Wu et al.
Fig. 1. SEM images of UiO-66 seeds (a) and seeded support (b, c), UiO-66 membranes prepared from in-situ synthesis (d, e) and secondary growth (f, g), XRD patterns (h) and EDX
mapping (i) of the UiO-66 membranes from secondary growth. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article.)
the growth of UiO-66 membranes. From our investigation, it is essential
that H2O is equal to ZrCl4 in the mother solution for a high quality UiO-
66 membrane. A little more or less would disturb the growth of the UiO-
66 crystals inside the membrane, leading to the preparation failure of
UiO-66 membranes.
3.2.2. Effect of acetic acid
It is reported that the addition of monocarboxylic acid ligands with
only one coordination site can promote crystal growth in a preferred
direction, due to the competition between the ligands and organic
linkers for coordination to the metal cations [49]. And thus acetic acid
as modulator was employed to regulate the formation of UiO-66 crys-
tals in the previous reference [46]. The results showed that both the
crystal size and the crystallinity of UiO-66 increased with increasing
amounts of acetic acid. Thus, it is perfectly logical and reasonable that
modulators may affect the formation of UiO-66 membranes. In the
following section, acetic acid was utilized as a modulator to investigate
its effect on the growth of UiO-66 membranes.
A series of UiO-66 membranes were prepared from the precursor
solution with different amounts of acetic acid, varying between 0 and
200 equivalents (eq) which refers to the molar ratios of acetic acid to
ZrCl4. The results of SEM and XRD measurements are shown in Fig. 3.
An amorphous phase can been discerned from cross-sectional view of
the membranes when no acetic acid or low concentration of acetic acid
(75 eq) is added (Fig. 3b and d), even though few cubic crystals or
octahedral particles are observed on the surface of the membranes
(Fig. 3a and c), and weak characteristic peaks of UiO-66 can be found in
the XRD pattern of the membrane (Fig. 3i). When the molar ratio of
acetic acid to ZrCl4 is increased to 150 eq, a dense crystalline membrane
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Journal of Membrane Science 544 (2017) 342–350
is clearly seen from the SEM images (Fig. 3e and f) and judged from the
XRD pattern. From the top view (Fig. 3e), the UiO-66 crystals with
octahedral shape are approximately 1–5 µm in size and intergrown very
well on the surface. The crystallinity of membranes is also enhanced
with increasing the amount of the acetic acid. Nevertheless, too much
acetic acid (200 eq) goes against the growth of the membrane and the
membrane thickness is not further increased (Fig. 3g and h).
Based on these results, it can be speculated that acetic acid is vital to
the formation of UiO-66 crystalline membranes. It is reported that
zirconium cations and the modulator acetic acid are likely to form
zirconium complexes whose structures are similar to the SBU in UiO-66
[50]. And there exits the competition between acetic acid and organic
linkers for coordination to the coordination sites of the zirconium ca-
tions, leading to a possible decrease in the formation of Zr-SBU by the
connection of acetic acid with zirconium cations. As a consequence, the
nucleation rates for UiO-66 particles decrease when acetic acid as a
modulator is added in the synthesis system, thus resulting in producing
larger crystals. Therefore, acetic acid added in the synthesis solution of
UiO-66 membranes mainly favors the crystalline growth of UiO-66
crystals. Moreover, acetic acid can also inhibit UiO-66 crystals growth
in the (111) direction, leading to the formation of octahedral crystalline
structures consisting of (111) surfaces [51]. That's the reason why the
UiO-66 membranes consist of octahedral crystals rather than cubic
lattices reported by Liu et al. [35]. This well explains the experimental
results that an amorphous membrane layer is easily produced when
there is no acetic acid or less amount of acetic acid in the synthesis
solution, while a crystalline UiO-66 membrane layer is obtained with
increasing the amount of acetic acid (no less than 150 eq). Besides,
what deserves to be mentioned is the substrates are of significance to
F. Wu et al.
Fig. 2. SEM images for the UiO-66 membranes prepared using mother solutions with different H2O/DMF molar ratios under the same synthesis condition (120 °C, 72 h)：H2O/DMF = 0
(a, b), 1:750 (c, d), 1:550 (e, f), 1:500 (g, h), 1:450 (i, j); XRD patterns of relevant membranes (k).
the formation of UiO-66 membrane and that may explain why we failed
to prepared a dense membrane as reported when no acetic acid was
added [35].
From the above investigation, it can be indicated that water and
acetic acid play different significant roles in the synthesis of UiO-66
membranes. Water can promote the nucleation and intergrowth of UiO-
66 nanocrystals, while acetic acid favors the crystallization and pre-
ferred growth of UiO-66 structure. Only water and acetic acid match
well in the synthesis solution, can a continuous UiO-66 crystalline
membrane be obtained.
3.3. PV performance of UiO-66 membranes
According to the report by Valenzano et al., UiO-66 crystals possess
hydrophilic surfaces [33]. We measured the water contact angle on the
surface of the UiO-66 membrane as shown in Fig. S3 in the Supporting
information. And the result confirms its hydrophilicity. Fig. 4 shows the
adsorption isotherm of methanol and MTBE over the UiO-66 powders
collected from the bottom of the autoclaves. Clearly, UiO-66 adsorbs
more methanol than MTBE, which is in line with our speculation that
UiO-66 membranes have preferential adsorption for methanol. More-
over, the pore size of UiO-66 (6 Å) lies between the kinetic diameter of
methanol (3.8 Å) and that of MTEB (6.3 Å)，so it can be predicted that
UiO-66 membranes are able to separate methanol molecules from larger
MTBE ones. That speculation was certified by pure component perva-
poration under 0.1 MPa at 40 °C, in which the methanol flux was
2.42 kg m−2 h−1 while the MTBE flux was only 0.45 kg m−2 h−1.
Thus, it is expected that UiO-66 membranes could give a high se-
lectivity of methanol over MTBE due to their hydrophilic property and
molecular sieving effect of UiO-66. So, here the UiO-66 membrane
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Journal of Membrane Science 544 (2017) 342–350
achieved under optimum synthesis condition was for the first time
applied in the separation of methanol/MTBE mixtures by PV process.
3.3.1. Pervaporation performance of the UiO-66 membranes
The single-component gas permeation was measured at ambient
temperature (20 °C). The H2 permeance is approximately 5.4 ×
10−7 mol m−2 s−1 Pa−1, and the ideal selectivity of H2/N2 and H2/CH4
are 8.2 and 11.4, which are higher than their corresponding Knudsen
selectivity values of 3.7 and 2.8, respectively. This indicates that the
membrane is compact. And the gas separation performance of our UiO-
66 membrane is comparable to several other reported UiO-66 mem-
branes [35,37,38].
Pervaporation separation of 5 wt% methanol/MTBE mixtures was
carried out at 40 °C, and was operated using vacuum as driving force,
keeping the downstream permeate pressure at 0.1 MPa. For the UiO-66
membrane with thickness of 6 µm, the membrane have a separation
factor of nearly 600 and a flux of 1.21 kg m−2 h−1, and the methanol
content in permeate can reach more than 96 wt%. This high separation
performance is in accordance with our expectations that UiO-66
membranes can separate methanol from MTBE.
In typical pervaporation processes, operating parameters such as
operating temperature and feed composition have great influences on
the performance of the membranes. Thus, the UiO-66 membrane with
thickness of 6 µm was selected as representative of the UiO-66 mem-
branes to investigate the impacts of operating temperature and feed
composition on the PV performance of UiO-66 membranes.
3.3.2. Effect of operating temperature
Fig. 5 presents the effects of operating temperature on the PV per-
formance of UiO-66 membranes for separating 5 wt% methanol/MTBE
F. Wu et al.
Fig. 3. SEM images of the UiO-66 membranes prepared in the presence of different molar equivalents (with respect to ZrCl4) of acetic acid, acetic acid/ZrCl4 = 0 (a, b), 75 eq (c, d), 150
eq (e, f), 200 eq (g, h); XRD patterns of relevant membranes (i).
Fig. 4. Single-adsorption isotherm of methanol and MTBE over the UiO-66 powders at
25 °C.
mixtures. It is obvious that permeation flux increases but the separation
factor decreases upon the increase of the operating temperature
(Fig. 5a). As operating temperature increases, the vapor pressure of feed
side increases, while the downstream permeate pressure remains un-
changed and thus the driving force for mass transfer increases [19].
Besides, the mobility of permeating molecules is also enhanced with
increasing operation temperature [52]. In all, the increased permeation
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Journal of Membrane Science 544 (2017) 342–350
flux is attributed to an increase in the driving force and mass transport
coefficients of the permeating components. While the decrease in se-
paration factor with increasing operating temperature can be explained
by the Arrhenius equation:
E
JP = A0 exp ⎛− P ⎞
⎝ RT ⎠ (5)
where Ep, Jp, A0, R and T are apparent activation energy (kJ mol−1),
permeation flux (kg m−2 h−1), pre-exponential factor, gas constant and
operating temperature (K), respectively.
According to Arrhenius equation, the higher the apparent activation
energy, the higher the temperature sensitivity of permeation flux was,
and the bigger increasing range of permeation flux [53]. Fig. 5b depicts
the Arrhenius plot for permeation flux vs temperature on the UiO-66
membrane for PV separation of 5 wt% methanol/MTBE mixtures. The
activation energy of MTBE value (31.45 kJ mol−1) is higher than that
of methanol (7.32 kJ mol−1), indicating that the MTBE permeation is
more dependent on operating temperature, resulting in a decrease in
separation factor at higher operational temperature [54].
The permeability of components and membrane selectivity were
counted out to further identify the influence of operating temperature.
As shown in Fig. 5c, both permeability of components and membrane
selectivity decrease upon the increase of the operating temperature.
Generally, sorption always decreases with increasing temperature,
while diffusivity usually increases. This indicates that in the PV se-
paration of UiO-66 membrane, sorption causes more changes than
diffusivity. In other words, sorption selectivity is dominant in the PV
process. And the decrease in selectivity can be attributed to the com-
bined effect of sorption and diffusion changes caused by the increasing
F. Wu et al.
Fig. 5. Effect of operating temperature on PV performance of UiO-66 membranes: (a)
total flux and separation factor; (b) temperature dependence of the permeation flux for PV
separation of 5 wt% methanol/MTBE mixtures; (c) methanol permeability, MTBE per-
meability and selectivity. (Operating conditions: down-stream pressure 0.1 MPa, me-
thanol feed solution 5 wt%.).
temperature. Although the decrease in membrane selectivity as the
temperature increases, the membrane still gives a high methanol/MTBE
selectivity. This may be attributed to the high preferential sorption of
the hydrophilic methanol compared to MTBE.
3.3.3. Effect of feed composition
All the experiments were carried out at operating temperature of
40 °C under the down-stream of 0.1 MPa. As shown in Fig. 6a, with the
increase of methanol concentration in feed, the total flux increases
348
Journal of Membrane Science 544 (2017) 342–350
Fig. 6. Effect of feed methanol content on separation performance of the UiO-66 mem-
brane: (a) total flux and separation factor; (b) methanol permeability, MTBE permeability
and selectivity. (Operating conditions: operating temperature 40 °C, down-stream pres-
sure 0.1 MPa.).
Fig. 7. Long-term pervaporation performance of the UiO-66 membrane. (Operating
conditions: operating temperature 40 °C, down-stream pressure 0.1 MPa, methanol feed
solution 5 wt%.).
continuously, while the separation factor decreases, which is coincident
with the trade-off law. As UiO-66 membrane is favorable for the ad-
sorption of methanol, the driving force of methanol transport increases
due to the higher methanol partial pressure caused by higher methanol
content in feed. The decrease of the separation factor may be explained
by the widening transport inside the membrane caused by the flexibility
of the UiO-66 framework. Besides, the flexibility also contributes to the
increase of flux. Fig. 6b presents the methanol and MTBE permeability
F. Wu et al.
Table 1
Comparison of PV performance of the UiO-66 membranes with the literature data for separating methanol/MTBE mixtures.
Membranes Feed (wt%) Feed temp (°C)
Plasma polymerized AA/PHB 20 40
NaCS/HDPC PELSC nanocomposite (SiO2) 14.33 51
NaCS/HDPC PELSC membrane 14.3 51
Cu2(bdc)2(bpy)n/SPES-C MMM 15 40
aSPES-C/PEI (0–20 wt%) 15 40
40PHB 20 50
PLA 1–87 30
UiO-66 5 40
15 40
and membrane selectivity of the UiO-66 membrane at different feed
methanol contents. It is obvious that the membrane has a decrease in
both methanol, MTBE permeability and methanol/MTBE selectivity as
the feed methanol content increases. The reduced permeability and
membrane selectivity may be due to the crowding or saturation effect of
methanol diffusion through the UiO-66 pores [55].
3.3.4. Stability of the UiO-66 membrane
Fig. 7 depicts the changes of permeation flux and separation factor
with operation time for separating 5 wt% methanol/MTBE mixtures at
40 °C. Fresh methanol/MTBE mixtures were added at intervals to the
feed tank to keep the feed concentration constant throughout the ex-
periment. During 72 h continuous operation, both the total flux and
separation factor hardly change, indicating that the UiO-66 membranes
possess structural stability required for long term PV operation. Fig. S4
in the Supporting information shows the XRD patterns and SEM images
of the UiO-66 membrane after long-term operation tests. The XRD re-
sult shows that the UiO-66 membrane retains its high crystallinity, in-
dicating that the UiO-66 membrane is stable in the pervaporation en-
vironment. What's more, as can be seen from SEM images, the UiO-66
membrane is dense and compact even after long-time pervaporation
operation. No cracks can be discerned and octahedral crystals remain
complete. Based on these facts, it comes to the conclusion that UiO-66
membranes inherit the outstanding chemical stability of UiO-66 struc-
ture. And this high chemical stability of UiO-66 membranes is expected
to be an advantage for the practical applications.
3.4. Comparison of PV performance with literature data
Table 1 summarizes the PV performance of membranes reported in
recent years and our UiO-66 membranes for separating methanol/
MTBE mixtures. Despite different operational conditions, the results in
this work have demonstrated that the PV performances of the UiO-66
membrane are comparable with other membranes, with higher flux and
moderate separation factor. Particularly, the flux of the membrane can
reach 1.21 kg m−2 h−1, being higher than most of the reported mem-
branes. Besides, for feed methanol content ranging from 10 to 30 wt%,
the UiO-66 membranes offer better separation performance than the
commercially available organo-selective membrane PERVAP 2256
[19]. What's more, the UiO-66 membranes show outstanding perfor-
mance among several other MOF membranes applied in PV separation
in the literature so far [56–60], especially stability. This high separation
performance combined with its high chemical stability suggests that
UiO-66 membranes should be promising candidates for the practical
application in pervaporation.
4. Conclusion
In conclusion, continuous and stable UiO-66 membranes were suc-
cessfully fabricated on macroporous α-Al2O3 tubes by employing the
secondary growth method. The crucial synthesis parameters including
water and acetic acid have a great impact on the membrane growth.
349
Journal of Membrane Science 544 (2017) 342–350
Flux (kg/(m2 h)) Separation factor Refs.
2.92–10.14 7.5–18.6 [61]
1.23 89 [62]
0.65 181 [55]
0.17 2300 [63]
0.22 1850 [64]
0.39 3.98 [65]
0.45 35 [66]
1.21 597 This work
1.92 147 This work
Water can promote the intergrowth of UiO-66 crystals and acetic acid
plays significant roles in promoting crystallization. Under the optimum
synthesis conditions, the obtained UiO-66 membrane with the thickness
of 6 µm shows excellent PV performance for separating 5 wt% me-
thanol/MTBE mixtures with high flux of 1.21 kg m−2 h−1 and a se-
paration factor of nearly 600. What's more, the membrane exhibits
highly stable PV performance due to the excellent chemical stability of
UiO-66 structure.
Our work as well as that of Liu et al. indicates that the UiO-66
membranes demonstrate excellent performance in liquid separation
processes such as pervaporation and desalination under harsh en-
vironments [35,36]. Those results imply that, thanks to their extra-
ordinary chemical and thermal stability, Zr-MOF based membranes
have great potential to be applied in industrial separation process in the
future. Studies are in progress to explore new types of Zr-based MOF
membranes and their new application fields aiming at practical appli-
cations.
Acknowledgments
The authors gratefully acknowledge the financial support from the
National Natural Science Foundation of China (Nos. 21476039, and
21076030).
Appendix A. Supporting information
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.memsci.2017.09.047.
References
[1] J. Yang, H.J. Kim, W.H. Jo, Y. Kang, Analysis of pervaporation of methanol-MTBE
through cellulose acetate and cellulose triacetate membranes, Polymer 39 (1998)
1381–1385.
[2] S. Sridhar, B. Smitha, A. Shaik, Pervaporation-based separation of methanol/MTBE
mixtures-a review, Sep. Purif. Technol. 34 (2005) 133.
[3] X. Wu, Q. Zhang, F. Soyekwo, Q. Liu, A.M. Zhu, Pervaporation removal of volatile
organic compounds from aqueous solutions using the highly permeable PIM-1
membrane, AIChE J. 62 (2016) 842–851.
[4] A. Mohammadi, J.P.G. Villaluenga, H.J. Kim, T. Chan, V. Rauw, Effects of polymer
solvents on the performance of cellulose acetate membranes in methanol/methyl
tertiary butyl ether separation, J. Appl. Polym. Sci. 82 (2001) 2882–2895.
[5] H. Wu, X. Fang, X. Zhang, Z. Jiang, B. Li, X. Ma, Cellulose acetate-poly (nvinyl-2-
pyrrolidone) blend membrane for pervaporation separation of methanol/MTBE
mixtures, Sep. Purif. Technol. 64 (2008) 183–191.
[6] Y. Wang, R. Yang, G. Luo, Y.Y. Dai, Preparation of cellulose acetate membrane filled
with metal oxide particles for the pervaporation separation of methanol/methyl
tert-butyl ether mixtures, Chem. Eng. J. 146 (2009) 6–10.
[7] L. Zhang, H. Chen, Z. Zhou, Y. Lu, C. Gao, Pervaporation of methanol/MTBE/ C5
ternary mixtures through the CA membrane, Desalination 149 (2002) 73–80.
[8] S. Cao, Y. Shi, G. Chen, Permeation behavior in cellulose triacetate dense membrane
during pervaporation separation of methanol/methyl tert-butylether mixtures,
Polym. Int. 49 (2000) 209–215.
[9] X. Ma, C. Hu, R. Guo, X. Fang, H. Wu, Z. Jiang, HZSM-5 filled cellulose acetate
membranes for pervaporation separation of methanol/MTBE mixtures, Sep. Purif.
Technol. 59 (2008) 34–42.
[10] J.W. Rhim, Y.K. Kim, Pervaporation separation of MTBE–methanol mixtures using
cross-linked PVA membranes, J. Appl. Polym. Sci. 75 (2000) 1699–1707.
[11] N.D. Hilmioglu, S. Tulbentci, Pervaporation of MTBE/methanol mixtures through
F. Wu et al.
PVA membranes, Desalination 160 (2004) 263–270.
[12] G. Gozzelino, Pervaporation of methanol/methyl-t-butyl ether mixtures through
poly (vinyl alcohol)/poly (acrylic acid) blend membranes, Sep. Purif. Technol. 40
(2005) 2265–2276.
[13] B. Cai, Y. Li, H. Yang, C. Gao, Effect of separating layer in pervaporation composite
membrane for MTBE/MeOH separation, J. Membr. Sci. 194 (2001) 151–156.
[14] S.G. Kim, Y.I. Kim, H.G. Yun, G.T. Lim, K.H. Lee, Preparation of asymmetric PVA
membranes using ternary system composed of polymer and cosolvent, J. Appl.
Polym. Sci. 88 (2003) 2884–2890.
[15] R.Y.M. Huang, G.Y. Moon, R. Pal, Chitosan/anionic surfactant complex membranes
for the pervaporation separation of methanol/MTBE and characterization of the
polymer/surfactant system, J. Membr. Sci. 184 (2001) 1–15.
[16] M. Niang, G. Luo, A triacetate cellulose membrane for the separation of methyl tert-
butyl ther/methanol mixtures by pervaporation, Sep. Purif. Technol. 24 (2001)
437–449.
[17] S. Ray, S.K. Ray, Synthesis of highly methanol selective membranes for separation
of methyl tertiary butyl ether (MTBE) /methanol mixtures by pervaporation, J.
Membr. Sci. 278 (2006) 279–289.
[18] M. Zhou, M. Persin, J. Sarrazin, Methanol removal from organic mixtures by per-
vaporation using poly pyrrole membranes, J. Membr. Sci. 117 (1996) 303–309.
[19] M. Peivasti, A. Madandar, T. Mohammadi, Effect of operating conditions on per-
vaporation of methanol/methyl tert-butyl ether mixtures, Chem. Eng. Process.
Intensif. 47 (2008) 1069–1074.
[20] H. Kita, T. Inoue, H. Asamura, K. Tanaka, O. Okamoto, NaY zeolite membrane for
the pervaporation separation of methanol–methyl tert-butyl ether mixtures, Chem.
Commun. 1 (1997) 45–46.
[21] M. Noacka, P. Kölscha, J. Caroa, M. Schneidera, P. Toussainta, I. Sieberb, MFI
membranes of different Si/Al ratios for pervaporation and steam permeation,
Microporous Mesoporous Mater. 35–36 (2000) 253–265.
[22] Z. Wang, I. Kumakiri, K. Tanaka, X. Chen, H. Kita, NaY zeolite membranes with high
performance prepared by a variable-temperature synthesis, Microporous
Mesoporous Mater. 182 (2013) 250–258.
[23] G. Férey, Hybrid porous solids: past, present, future, Chem. Soc. Rev. 37 (2008)
191–214.
[24] S. Horike, S. Shimomura, S. Kitagawa, Soft porous crystals, Nat. Chem. 1 (2009)
695–704.
[25] J. Tan, A.K. Cheetham, Mechanical properties of hybrid inorganic–organic frame-
work materials: establishing fundamental structure–property relationships, Chem.
Soc. Rev. 40 (2011) 1059–1080.
[26] K. Huang, X. Dong, R. Ren, W. Jin, Fabrication of homochiral metal-organic fra-
mework membrane for enantio separation of racemic diols, AIChE J. 59 (2013)
4364–4372.
[27] L. Murray, M. Dincă, J. Long, Hydrogen storage in metal–organic frameworks,
Chem. Soc. Rev. 38 (2009) 1294–1314.
[28] A. Rui, J.B. James, A. Kasik, Y. Lin, Metal-organic framework membrane process for
high purity CO2 production, AIChE J. 62 (2016) 3836–3841.
[29] A. Corma, H. Garcia, I. Llabres, F.X. Xamena, Engineering metal organic frame-
works for heterogeneous catalysis, Chem. Rev. 110 (2010) 4606–4655.
[30] A.E. Elda, K.A. Ahmet, S. Keskin, Opportunities and challenges of MOF-based
membranes in gas separations, Sep. Sci. Technol. 152 (2015) 207–237.
[31] J.H. Cavka, S. Jackobsen, U. Olsbye, N. Guillou, C. Lamberti, S. Bordiga,
K.P. Lillerud, A new zirconium inorganic building brick forming metal organic
frameworks with exceptional stability, J. Am. Chem. Soc. 130 (2008)
13850–13851.
[32] H. Furukawa, F. Gandara, Y. Zhang, J. Jiang, W.L. Queen, M.R. Hudson,
O.M. Yaghi, Water adsorption in porous metal–organic frameworks and related
materials, J. Am. Chem. Soc. 136 (2014) 4369–4381.
[33] L. Valenzano, B. Civalleri, S. Chavan, S. Bordiga, M.H. Nilsen, S. Jakobsen,
K.P. Lillerud, C. Lamberti, Disclosing the complex structure of UiO-66 metal organic
framework: a synergic combination of experiment and theory, Chem. Mater. 23
(2011) 1700–1718.
[34] K. Leus, T. Bogaerts, J.D. Decker, H. Depauw, K. Hendrickx, H. Vrielinck,
V.V. Speybroeck, P.V.D. Voort, Systematic study of the chemical and hydrothermal
stability of selected “stable” metal organic frameworks, Microporous Mesoporous
Mater. 226 (2016) 110–116.
[35] X. Liu, N.K. Demir, Z. Wu, K. Li, Highly water-stable zirconium metal-organic fra-
mework UiO-66 membranes supported on alumina hollow fibers for desalination, J.
Am. Chem. Soc. 137 (2015) 6999–7002.
[36] X. Liu, C. Wang, B. Wang, K. Li, Novel organic-dehydration membranes prepared
from zirconium metal-organic frameworks, Adv. Funct. Mater. 27 (2017) 1604311.
[37] S. Friebe, Be. Geppert, F. Steinbach, J. Caro, Metal−organic framework UiO-66
layer: a highly oriented membrane with good selectivity and hydrogen permeance,
ACS Appl. Mater. Interfaces 14 (2017) 12878–12885.
[38] M. Miyamoto, K. Hori, T. Goshima, N. Takaya, Y. Oumi, S. Uemiya, An organose-
lective zirconium-based metal–organic-framework UiO-66 membrane for perva-
poration, Eur. J. Inorg. Chem. 14 (2017) 2094–2099.
[39] G. Lu, C. Cui, W. Zhang, Y. Liu, F. Huo, Synthesis and self-assembly of mono-
dispersed metal-organic framework, Chem. Asian J. 8 (2013) 69–72.
[40] L. Chai, J. Yang, J. Lu, D. Yin, Y. Zhang, Ethanol perm-selective B-ZSM-5 zeolite
membranes from dilute solutions, AIChE J. 62 (2016) 2447–2458.
350
Journal of Membrane Science 544 (2017) 342–350
[41] L. Kong, X. Zhang, H. Liu, J. Qiu, Synthesis of a highly stable and scalable ZIF-8
membrane on a macroporous ceramic tube by manual-rubbing ZnO deposition as a
multifunctional layer, J. Membr. Sci. 490 (2015) 354–363.
[42] R.W. Baker, J.G. Wijmans, Y. Huang, Permeability, permeance and selectivity: a
preferred way of reporting pervaporation performance data, J. Membr. Sci. 348
(2010) 346–352.
[43] X. Zhang, Y. Liu, L. Kong, H. Liu, J. Qiu, W. Han W, T. Weng, K. Yeung, W. Zhu, A
simple and scalable method for preparing low-defect ZIF-8 tubular membranes, J.
Mater. Chem. A 1 (2013) 10635–10638.
[44] R. Ranjan, M. Tsapatsis, Microporous Metal organic framework membrane on
porous support using the seeded growth method, Chem. Mater. 21 (2009)
4920–4924.
[45] J. Liu, N. Canfield, W. Liu, Preparation and characterization of a hydrophobic
metal-organic framework membrane supported on a thin porous metal sheet, Ind.
Eng. Chem. Res. 55 (2016) 3823–3832.
[46] A. Schaate, P. Roy, A. Godt, J. Lippke, F. Waltz, M. Wiebcke, P. Behrens, Modulated
synthesis of Zr-based metal–organic frameworks: from nano to single crystals,
Chem. Eur. J. 17 (2011) 6643–6651.
[47] G. Wismann, A. Schaate, S. Lilienthal, L. Bremer, A.M. Schneider, P. Behrens,
Modulated synthesis of Zr-fumarate MOF, Microporous Mesoporous Mater. 152
(2012) 64–70.
[48] G.N. Karanikolos, J.W. Wydra, J.A. Stoeger, H. Garcı´, A. Corma, M. Tsapatsis,
Continuous c-oriented AlPO4−5 films by tertiary growth, Chem. Mater. 19 (2007)
792–797.
[49] T. Tsuruoka, S. Furukawa, Y. Takashima, K. Yoshida, S.J. Isoda, S. Kitagawa,
Nanoporous nanorods fabricated by coordination modulation and oriented attach-
ment growth, Angew. Chem. Int. Ed. 48 (2009) 4739–4743.
[50] P. Piszczek, A. Radtke, A. Grodzicki, A. Wojtczak, J. Chojnacki, The new type of
[Zr6(μ3-O)4(μ3-OH)4] cluster core: crystal structure and spectral characterization of
[Zr6O4(OH)4(OOCR)12, Polyhedron 26 (2007) 679–685.
[51] M. Miyamoto, S. Kohmura, H. Iwatsuka, Y. Oumi, S. Uemiya, In situ solvothermal
growth of highly oriented Zr-based metal organic framework UiO-66 film with
monocrystalline layer, Cryst. Eng. Commun. 17 (2015) 3422–3425.
[52] M. Tamaddondar, H. Pahlavanzade, H.S. Saeid, G. Ruan, N. Tan, Self-assembled
polyelectrol-te surfactant nano composite membranes for pervaporation separation
of MeOH/MTBE, J. Membr. Sci. 472 (2014) 91–101.
[53] G. Liu, Z. Jiang, K. Cao, S. Nairc, X. Cheng, J. Zhao, H. Goma, H. W, F. Pan,
Pervaporation performance comparison of hybrid membranes filled with two-di-
mensional ZIF-L nanosheets and zero-dimensional ZIF-8 nanoparticles, J. Membr.
Sci. 523 (2017) 185–196.
[54] S.Y. Nam, Y.M. Lee, Pervaporation separation of methanol/methyl. t-butyl ether
through chitosan composite membrane modified with surfactants, J. Membr. Sci.
157 (1999) 63–71.
[55] J. Zhao, F. Pan, P. Li, C. Zhao, Z. Jiang, P. Zhang, X. Cao, Fabrication of ultrathin
membrane via layer-by-layer self-assembly driven by hydrophobic interaction to-
wards high separation performance, ACS Appl. Mater. Interfaces 5 (2013)
13275–13283.
[56] A. Kasik, J. James, Y. Lin, Synthesis of ZIF-8 membrane on a ZnO modified ɑ-Al2O3
support by a modified reactive seeding method, Ind. Eng. Chem. Res. 55 (2016)
2831–2839.
[57] M.M. Anne, T. Daniel, J. Kenneth, J. Balkus, Fabrication of a substituted imidazo-
late material (SIM-1) membrane using post synthetic modification (PSM) for per-
vaporation of water/ethanol mixtures, J. Porous Mater. 22 (2015) 1275–1284.
[58] L. Fan, M. Xue, Z. Kang, G. Wei, L. Huang, J. Shang, D. Zhang, S. Qiu, ZIF-78
membrane derived from amorphous precursors with permselectivity for cyclohex-
anone/cyclohexanol mixture, Microporous Mesoporous Mater. 192 (2014) 29–34.
[59] X. Dong, Y. Lin, Synthesis of an organophilic ZIF-71 membrane for pervaporation
solvent separation, Chem. Commun. 49 (2013) 1196–1198.
[60] L. Diestel, H. Bux, W.D. Dennis, J. Caro, Pervaporation studies of n-hexane, ben-
zene, mesitylene and their mixtures on zeolitic imidazolate framework-8 mem-
branes, Microporous Mesoporous Mater. 164 (2012) 288–293.
[61] M. Villegas, A.I. Romero, M.L. Parentis, E.F. Vidaurre, J.C. Gottifredi, Acrylic acid
plasma pomy-merizedpoly(3-hydroxybutyrate) membranes for methanol/MTBE
separation by pervaporation, Chem. Eng. Res. Des. 109 (2016) 234–248.
[62] G. Han, P. Xu, K. Zhou, Q. Zhang, A. Zhu, Q. Liu, Fluorene-containing poly(arylene
ether sulfone) block copolymers: synthesis, characterization and application, J.
Membr. Sci. 464 (2014) 72–79.
[63] G. Han, K. Zhou, A. Lai, Q. Zhang, A. Zhu, Q. Liu, [Cu2(bdc)2(bpy)]n/SPES-C mixed
matrix membranes for separation of methanol/methyl tert-butyl ether mixtures, J.
Membr. Sci. 454 (2014) 36–43.
[64] G. Han, Y. Gong, Q. Zhang, A. Zhu, M. Ye, Q. Liu, Facile preparation of homo-
geneous polyelectrolyte complex membranes for separation of methanol/methyl
tert-butyl ether mixtures, J. Membr. Sci. 447 (2013) 246–252.
[65] M. Villegas, E.F.C. Vidaurre, A.C. Habert, J.C. Gottifredi, Sorption and pervapora-
tion with poly (3-hydroxybutyrate) membranes: methanol/methyl tert-butyl ether
mixtures, J. Membr. Sci. 367 (2011) 103–109.
[66] S. Zereshki, A. Figoli, S.S. Madaeni, S. Simone, E. Driol, Pervaporation separation of
methanol/methyl tert-butyl ether with poly(lactic acid) membranes, J. Appl.
Polym. Sci. 118 (2010) 1364–1371.