See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/325434883

ZIF-67 filled PDMS mixed matrix membranes for recovery of ethanol via
pervaporation

Article  in  Separation and Purification Technology · May 2018

DOI: 10.1016/j.seppur.2018.05.055

CITATION READS

1 245

9 authors, including:

Amin Khan Mazhar Gilani

Zhejiang University COMSATS University Islamabad
10 PUBLICATIONS   4 CITATIONS    38 PUBLICATIONS   237 CITATIONS   

SEE PROFILE SEE PROFILE

Zabia Sajjad Asim Laeeq Khan

COMSATS University Islamabad COMSATS University Islamabad
1 PUBLICATION   1 CITATION    42 PUBLICATIONS   782 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Seismic Exploration View project

Phase Inversion View project

All content following this page was uploaded by Amin Khan on 07 June 2018.

The user has requested enhancement of the downloaded file.

 Separation and Purification Technology 206 (2018) 50–58

Contents lists available at ScienceDirect

Separation and Purification Technology

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

ZIF-67 filled PDMS mixed matrix membranes for recovery of ethanol via T
pervaporation
⁎
Amin Khana, Mohsin Alia, Ayesha Ilyasa, Parimal Naikb, Ivo F.J. Vankelecomb, ,
⁎
Mazhar Amjad Gilanid, Muhammad Roil Biladc, Zabia Sajjada, Asim Laeeq Khana,
a
Department of Chemical Engineering, COMSATS University Islamabad, Lahore Campus, Pakistan
b
Center of Surface Chemistry and Catalysis, Faculty of Bioscience Engineering, KU Leuven, Belgium
c
Chemical Engineering Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 32610 8 Perak, Malaysia
d
Department of Chemistry, COMSATS University Islamabad, Lahore Campus, Pakistan

A R T I C LE I N FO A B S T R A C T

Keywords: Zeolitic imidazole frameworks (ZIFs), a subclass of metal organic frameworks (MOFs), are composed of metal
ZIF-67 ions linked by organic ligands which offer an exceptionally high surface area and appealing separation potential.
Pervaporation In this study, mixed matrix membranes (MMMs) were prepared using polydimethylsiloxane (PDMS) as a hy-
MMM drophobic polymer and ZIF-67 as inorganic filler particle. ZIF-67 particles and MMMs were characterized by
PDMS
XRD, SEM, FTIR, BET and contact angle measurements. The prepared membranes were tested for the separation
Ethanol
of ethanol/water mixtures via pervaporation. Compared to unfilled PDMS membranes, MMMs loaded with 20 wt
% ZIF-67 showed an increase in flux and a doubled separation factor. The easy synthesis of ZIF-67 and its
enhanced separation performance make ZIF-67 an attractive candidate to prepare MMMs for a variety of
membrane applications.

1. Introduction
The excessive use of fossil fuels has caused serious environmental
problems. Clean and renewable bio-fuels are listed as promising alter-
natives to fossil fuels. Bio-ethanol is currently regarded as a valuable
liquid bio-fuel but the process which converts biomass to ethanol is
energy intensive and involves high processing costs [1,2]. The ethanol
concentration can range from 1 to 15 wt% in the fermentation broth,
which usually depends on the type of biomass source, yeast and hy-
drolysis procedure [3]. To obtain fuel-grade ethanol, water contents
should be less than 1–3 wt% [4]. Among the various purification pro-
cesses, such as distillation, adsorption, membrane distillation, and li-
quid-liquid extraction, pervaporation is an energy-saving and cost-ef-
fective process to separate ethanol from ethanol/water mixture.
Pervaporation has emerged as a promising technique holding the po-
tential to save up to 50% energy in contrast to conventional distillation
[5]. Despite its numerous advantages, pervaporation has difficulties to
find its way into industrial separations due to several limitations, such
as low flux, poor separation performance and stability of the membrane
material.
Among the materials used for pervaporation, PDMS is the most
widely used polymeric material. [6,7]. It shows very good thermal,
chemical and mechanical stability along with the high hydrophobicity
required for liquid separations [8–10]. The use of PDMS as a material
for pervaporation is limited by its low intrinsic selectivity that does not
meet the commercial demands [11]. The performance of PDMS can be
further enhanced by incorporation of porous fillers to form mixed
matrix membranes (MMMs) [14–19]. These membranes combine the
advantageous properties of polymeric and inorganic filler materials to
form a highly selective and permeable membrane. Despite their proven
advantage in improving separation performance, the incompatibility of
inorganic and polymeric phase, resulting into non-selective interfacial
voids, often limits the true exploitation of MMMs [12–14].
Metal organic frameworks (MOFs) are a new class of porous mate-
rials that have been considered as excellent fillers for the preparation of
MMMs. The presence of organic linkers coordinated to transition metal
ions provides good interfacial adhesion with the polymer matrix.
Recent studies showed that zeolitic imidazolate frameworks (ZIFs), a
subclass of MOFs, have superior thermal and chemical stability with
potential use in gas separation, catalysis, drug delivery, sensing and
electronic devices [15]. Previously, a number of MOFs, such as ZIF-8,
ZIF-71 and MIL-53, have been incorporated in a PDMS matrix to im-
prove the recovery of bio-alcohols [16–23] but the major drawback of
these particles were compromising either the flux or separation factor

⁎
Corresponding authors.
E-mail addresses: ivo.vankelecom@biw.kuleuven.be (I.F.J. Vankelecom), alaeeqkhan@ciitlahore.edu.pk (A.L. Khan).

https://doi.org/10.1016/j.seppur.2018.05.055
Received 23 April 2018; Received in revised form 28 May 2018; Accepted 28 May 2018
Available online 29 May 2018
1383-5866/ © 2018 Elsevier B.V. All rights reserved.
A. Khan et al.
in terms of separation performance. An ideal pervaporation membrane
should have superior flux and separation factor at the same time with
good durability and mechanical stability. Many studies have been
performed to minimize the tradeoff nature of pervaporation mem-
branes. These studies explained that the separation performance of
these membranes can be enhanced by increasing the hydrophobic
nature of the incorporated particles. In this respect, Wang et al. tried to
enhance the hydrophobicity of the used particles [24] but the obtained
results were not satisfactory in terms of performance parameters (flux
and separation factor). In this study, ZIF-67 was chosen as a filler ma-
terial for the synthesis of MMMs to obtain satisfactory performance.
Incorporation of a hydrophobic material in a hydrophobic polymer,
such as PDMS, is expected to increase affinity for alcohol molecules
resulting in an improved separation performance. ZIF-67 (Co(Hmim)2)
is synthesized by bridging cobalt cations with 2-methylimidazolate
anions, resulting in a sodalite topology. It was selected due to its su-
perior stability and high surface area (1240 m2/g). In addition, the
hydrophobicity of synthesized ZIF-67 particles would preferentially
allow ethanol to diffuse through the pores [25]. ZIF-67 is iso-structural
(framework structure and organic ligands) to ZIF-8, but has different
metal atoms i.e. Co. Another advantage is its convenient synthesis
under room temperature conditions in contrast to e.g. the hydrothermal
synthesis of zeolites [26]. It is expected that by incorporating highly
hydrophobic ZIF-67 particles will eventually help the easy sorption of
ethanol molecules. Apart from easy sorption, the overall flux of the
membrane will also be higher due to the small size and porous structure
ZIF-67 particles.
In present work, hydrophobic ZIF-67 particles were incorporated as
fillers in PDMS to prepare MMMs in order to improve the separation
properties of these membranes. Ethanol recovery from an aqueous
mixture was chosen as application to test the performance of the ZIF-
67/PDMS MMM for pervaporation.
2. Experimental
2.1. Materials
P-84 polyimide (PI) powder was purchased from HP polymer
(Austria), toluene and methanol from VWR international (UK), methyl
isobutyl ketone and isopropanol (IPA) from BDH laboratory supplies
(England) and Sigma-Aldrich respectively, N-methyl pyrrolidinone
(NMP) and tetrahydrofuran (THF) from Merck (Germany), PDMS pre-
polymer and cross-linker (RTV 615 A and B) from Techsil (UK), 2-
methylimidazole (99.0%) and cobalt nitrate hexahydrate Co
(NO3)2·6H2O from Acros Organics and Fischer Chemicals respectively.
2.2. Synthesis of ZIF-67 nanoparticles
ZIF-67 crystals were prepared in accordance with the literature
[26]. In a typical synthesis, 0.35 g of cobalt nitrate hexahydrate Co
(NO3)2·6H2O was dissolved in 11.3 g of methanol. 2-methylimidazole
(0.66 g) was dissolved in 11.3 g of methanol separately. The prepared
solutions were mixed and stirred continuously for 2 h at room tem-
perature to yield purple crystals. The mother liquid was centrifuged at
3500 rpm for 20 min, decanted and several times washed with me-
thanol. The obtained crystals were dried overnight at 85 °C.
2.3. Preparation of composite MMMs
The phase inversion technique was used to prepare a porous support
layer from a polymer dope solution. PI dope solution (15 wt% PI, 2 wt%
H2O, 62.25 wt% NMP and 20.75 wt% THF) was prepared and casted on
a non-woven polypropylene/polyethylene fabric (Novatex-2471) using
an automatic film applicator (HTML, Belgium) [19]. After an eva-
poration time of 30 s, the cast film was immersed in deionized water for
10 min at room temperature. The membrane formed by this process was
51
Separation and Purification Technology 206 (2018) 50–58
post-treated by a sequential solvent exchange. This was done by im-
mersing the support in IPA (3 h) and then in a mixture of MIBK, toluene
and oil in a 40:40:20 (v/v) composition for 3 days. The support was
subsequently dried at 65 °C for 1 h.
The composition of the solvent mixture was found to be critical in
obtaining a homogenous dispersion of filler particles in the membrane
matrix. Different ratios of both solvents were screened to evaluate the
effect on filler dispersion. An 80:20 composition of toluene-hexane re-
sulted in an optimum dispersion, even at the highest filler loading. The
selective layer of PDMS was coated on the support using a dip-coating
technique. A 15 wt% PDMS solution in toluene and hexane (80:20)
comprising of RTV 615 A and 615B in a 10:1 ratio was pre-crosslinked
for 2 h at 60 °C. To prepare MMMs, coating solutions were loaded with
different filler concentrations (5 wt%, 10 wt%, 15 wt% and 20 wt%),
stirred and sonicated for 15 min each (3 times). This sonication of ZIF-
67 filled PDMS mixtures is very important as this will hinder the ag-
gregation of ZIF-67 particle in the polymer matrix.
In order to coat a PDMS layer, the support plate was kept at an angle
of 60° and PDMS solution was poured on the support. This step was
repeated at least three times allowing solvents to evaporate for 5 min in
between. The cross-linking was completed in an oven at 110 °C for 24 h.
2.4. Pervaporation experiments
The separation performance of the synthesized membranes was
measured using a custom-built pervaporation unit. A schematic dia-
gram of the set-up is shown in Fig. 1. The experiments were conducted
with a 6 wt% aqueous ethanol solution at the selected temperature
range of 40–70 °C using a thermo-stated water bath. A cross-flow per-
vaporation module (CF016, Sterlitech) was used. The effective mem-
brane area was 16 cm2. Before running the experiments, the membranes
were kept in contact with feed solution for 10 h to reach steady state.
The feed was pumped by a peristaltic pump at a continuous volumetric
flow rate of 1 L/min at atmospheric pressure. The retentate was sent
back to the feed tank for recycling purpose. A vacuum pump was used
at the permeate side to maintain the vacuum. The permeate vapors
were condensed in a cold trap to obtain a liquid permeate samples
which were analyzed by a gas chromatograph (7890A, Agilent, USA)
equipped with a thermal conductivity detector. The permeate flux was
calculated by using Eq. (1)
Q
J=
At (1)
where J is the flux in kg/m h, Q is the permeate flow rate and t is the
2
time in h. Membrane separation factor (βi/j) was calculated by the ratio
of mole fractions of two components in the upstream (y) and down-
stream (x) as shown in Eq. (2):
yi / yj
βi / j =
x i / xj (2)
2.5. Membrane uptake
The membrane uptakes of the free-standing MMMs were measured
by immersing them in particular solvent. The free-standing films were
prepared by pouring a dispersion of PDMS/ZIF-67 into a flat bottom
glass petri-dish. The solution was placed in the oven at 70 °C for 12 h.
The dried pieces of PDMS films with different filler loadings were im-
mersed in the solvent for 48 h. The excess solution was quickly wiped
off using filter paper. After the equilibrium was established, films were
weighed on the electronic balance to calculate the difference between
weight before and after immersion in solvents. The uptake was calcu-
lated using the following equation:
Ws−Wd
Membrane uptake =
Wd (3)
A. Khan et al.
Fig. 1. Custom-made Pervaporation Set-up.
where Ws and Wd are the measured weights of the swollen and dry
membranes, respectively.
2.6. Density measurement
The densities of the membranes were experimentally determined
using a gas pycnometer (G-DenPyc 2900, Gold App Instruments). The
obtained values were compared with the theoretically calculated den-
sities. The fractional free volume (FFV) of the free standing PDMS film
was calculated using the group contribution method with the expres-
sion given below:
(V−1.3Vw)
FFV =
V (4)
3
where V (cm ) is the specific volume of the polymer, obtained by ex-
perimentally determined densities, and Vw is the van der Waals volume
calculated by group contribution method.
The FFV of MMMs was calculated from the following expression:
FFV =
V−⎡
⎣
( 1.3Vw
M ) (1−φZIF67 ) ( )
+ φZIF67 ⎤
ρZIF71
⎦ were consistent to the reported peaks of ZIF-67 [27]. Also, all present
V (5)
3 peak positions calculated from the known crystal structures. It could
where V (cm ) is the specific volume of the MMM obtained experi-
mentally, M is the molecular weight of polymer (g/mol) and φZIF67 is the
volume fraction of the filler in the MMM. The volume fraction of the
filler is calculated using the following equation:
wZIF / ρZIF 67
φZIF =
(1−wZIF )/ ρPDMS + WZIF / ρZIF 67
where wZIF is the weight fraction of filler particles in membranes, ρPDMS
and ρZIF67 are the densities (g cm−3) of PDMS and ZIF-67 respectively.
The theoretical densities are calculated from the following equation:
1 glomerates. Moreover, the average diameter of the ZIF-67 particles was
ρt =
(1−wZIF 67)/ ρZIF 67 + wZIF 67/ ρZIF 67
2.7. Characterization
A PANalytical X-ray Diffraction Spectrometer was used to obtain
XRD patterns of the filler using Cu-Kα radiation at 45 kV and 40 mA.
The morphology of the crystals and membranes were observed using
TESCAN Vega LMU – Variable pressure Scanning Electron Microscope
(SEM). The membrane samples were fractured by immersing them into
liquid nitrogen, and were sputtered with gold to increase their
Separation and Purification Technology 206 (2018) 50–58
conductivity. Brunauer-Emmett-Teller (BET) surface area and pore vo-
lume of the nanocrystals were calculated by Tristar II 3020 having a
temperature range from ambient to 425 °C. The contact angle mea-
surements were performed using a contact angle analyzer DSA-30
(KRUSS Germany). For measurements, contact liquid (distilled water
and ethanol) were dropped on the surface at different points. The
measurements were repeated three times and average of the measure-
ments was reported. The functional groups present in the samples were
confirmed by Thermo-Nicolet 6700P FTIR-Spectrometer (USA).
Thermal stability of the sample was determined by SDT Q600 TGA/DSC
(TA Instruments) with a ramp rate of 10 °C/min from 40 °C to 800 °C.
3. Results and discussion
3.1. Characterization of ZIF-67
The crystalline structure of the as-synthesized particles was con-
firmed by X-ray Diffraction (XRD) analysis as shown in Fig. 2. The
characteristic diffraction peaks showed that the synthesized particles
peaks index to a sodalite structure and show excellent agreement with
also be seen from the power X-ray diffraction pattern of the sample that
its free from water and other impurities does not exhibit substantial
changes in the XRD planes which validated that the particles were
successfully synthesized and well developed.
The morphology of the ZIF-67 crystals was determined by SEM
(6) pictures, as shown in Fig. 3. It can be seen that SEM results showed
partial agglomeration of the particles which may generate poor com-
patibility of the particles with polymer matrix resulting in the reduced
selectivity. Therefore, the prepared ZIF-67 filled PDMS mixtures were
well-sonicated prior to coating process to ensure the removal of ag-
(7) approximately 200 nm. The small particle size is expected to promote
homogenous distribution of the particles in the MMMs.
An FTIR spectrum was obtained to confirm the functional groups
present in the ZIF-67 particles (Fig. 4). The peaks were primarily at-
tributed to the 2-methylimidazole ligand. The positions of the peaks
correspond well with previous work [27]. The peaks ranging from 600
to 1500 cm−1 were due to the stretching and bending of the imidazole
group. A minor peak at 1448 cm–1 was due to the stretching mode of
C]N bonding in 2-MIM. The peaks obtained at 2929 and 3135 cm–1
were attributed to the stretching of CeH from the aliphatic methyl
group and aromatic ring of 2-MIM, respectively.
52
A. Khan et al. Separation and Purification Technology 206 (2018) 50–58

The BET surface area and the pore volume was derived from ni-
trogen physisorption measurements. Table 1 presents the pore structure
information. The high surface area and pore volume obtained in this
study is expected to promote the flux through the prepared MMMs.
TGA analysis was done to check the thermal stability of ZIF-67
particles (Fig. 5). The TGA curve showed gradual weight loss up to
3.5% from 100 to 200 °C. The gradual weight loss above 200 °C could be
due to the escape of residual solvent from the filler particle pores or
may be due to the presence of unreacted linker or partial solvent ma-
terial. It should also be noted that if any unreacted linker or solvent is
present it can result in the formation of hydrogen bond with water
which can eventually reduce the separation factor of the membranes.
On the other hand, the unreacted linker may also perform any side
reaction with polymer chain which in turn will affect the membrane
performance. The analysis also showed that the ZIF-67 structure re-
mained stable up to 200 °C. Beyond this temperature, it starts to gra-
dually decompose. This showed that the prepared particles were ther-
mally stable and could be used under the operating conditions of
pervaporation. These thermally stable ZIF-67 particles will increase the
thermal stability of the membranes. As clear from the TGA results that
ZIF-67 particles are quite thermally stable so it is expected that these
particles will improve the thermal properties by adsorbing the thermal
energy which will hinder the thermal attack and in a result the mem-
brane will become more stable.

3.2. Characterization of MMMs

Pervaporation follows the solution-diffusion mechanism involving a

Fig. 2. Powder XRD of ZIF-67 nanoparticles (a) synthesized (b) literature.
three-step process, i.e. sorption-diffusion-desorption. The hydro-
phobicity of the material plays an important role in improving the
sorption selectivity for alcohol/water mixtures. The results of contact
angle measurements of MMMs are presented in Table 2. The static
water and ethanol contact angle of pristine PDMS membrane was 108°
and 11° respectively. The increase in ZIF-67 loading led to an increase
in water contact angle from 108° to 137° while the contact angle of
ethanol decreased to 7° and 5° at 5% and 10% loading respectively.
Increased loading of ZIF-67 did not show any additional effect on the
ethanol contact angle. The incorporation of ZIF-67 particles had also
increased the surface roughness which resulted in the increase of con-
tact angle. This improved surface roughness helped in the enhancement
of non-polarity of the membranes resulting in the higher contact angle.
These results showed that addition of the filler enhanced the overall
hydrophobicity of the membrane matrix, and hence it can be assumed
that MMMs will show high affinity towards ethanol.
The cross-sectional SEM images of the MMMs show a dense top
layer without any visible signs of filler aggregation (Fig. 6). Fig. 6(g)
shows wrinkles on the PDMS surface which might have appeared due to
the shrinkage during post curing which is unavoidable and un-
controllable.

3.3. Pervaporation performance of MMMs

The uptake of the MMMs in ethanol was measured to investigate the

effect of incorporation of ZIF-67 particles. At least three membrane
coupons were tested to ensure true representation of the results and
measurements were repeated three time to evaluate the reproducibility.
Unfilled PDMS showed ethanol uptake of 0.85 ml/g (Fig. 7), while it get
reduced upon incorporation of ZIF-67 in the PDMS matrix. Similar
trend could also be found in the literature [28–30]. When filler and
polymer show good compatibility, the presence of filler particles in the
matrix induces swelling stability at the polymer-filler interface, leading
to reduced void spaces. This causes a decrease in the overall uptake
Fig. 3. SEM image of ZIF-67. capacity of the MMMs matrix [19].
The stability of ZIF-67 in water is also a concern for its application
in a feed containing significant proportion of water. Zhou et el. reported
this limitation of water stability of ZIF-67 in their study [30]. In order

53
A. Khan et al. Separation and Purification Technology 206 (2018) 50–58

Fig. 4. FTIR spectrum of ZIF-67 particles.

Table 1 of the samples after different time intervals. The intensity of reflections
BET surface area and pore volume of ZIF-67 crystals. is gradually decreasing with the passage of time due to the reduction in
BET surface area (m2/g) 1245 crystallinity. The results confirmed that ZIF-67 particles retained their
BJH Adsorption cumulative volume of pores (cm3/g) 0.665 crystalline structure when incorporated in chemically stable PDMS
matrix even after 21 days.
The pervaporation performance of the MMMs with different filler
loadings was evaluated for 6 wt% aqueous ethanol solution (Fig. 9). At
100 least three samples of each membranes were cut and tested for their
performance in pervaporation cell. The average of the obtained values
are reported. The incorporation of fillers in the PDMS matrix led to a
80
simultaneous increase in total flux and separation factor. Compared to
pristine PDMS membranes, membranes filled with 20% ZIF-67 showed
Weight loss (%)

60 a triple increase in flux and twice in separation factor at 40 °C. The

addition of highly porous filler in the polymer matrix amplifies the
sorption capacity of the membranes due to the available extra pore
40 volume sites, leading to an enhanced total membrane flux. The quan-
titative results of the FFV presented in Table 3 show indeed that the
addition of filler increased the FFV from 0.18 to 0.20. The addition of
20
hydrophobic ZIF-67 crystals simultaneously enhanced the overall hy-
drophobicity (Table 2), thus promoting the selective sorption of ethanol
0
molecules. The higher the concentration of ZIF-67 in membrane matrix,
100 200 300 400 500 600 700 the greater are the ethanol flux and the separation factor. An opposite
T(°C) trend can be observed from the results of ethanol uptake and total flux
(Figs. 7 and 9). The increase in total flux is possibly due to the per-
Fig. 5. TGA curve for ZIF-67. meation of water molecules along with the permeating ethanol due to
the kinetic diameter of water molecule (0.27 nm) that is less than the
Table 2 aperture size of ZIF-67 particle (0.43 nm).
Water and ethanol contact angle of the membranes. An investigation of the effect of feed temperature from 40 °C to 70 °C
on flux and separation factor was also carried out (Figs. 10 and 11).
Membrane Filler loading Water contact angle Ethanol contact angle
(%) (°) (°)
Both unfilled PDMS and the MMMs showed overall increase in the total
flux of up to 0.1429 while the separation factor decreased to 0.1254.
Pristine PDMS 0 108 11 ± 0.25 Increasing the temperature will result in an increased free volume due
MMM-05 5 113 7 ± 0.1 to additional thermal movement of polymer chains. The increase in
MMM-10 10 120 5 ± 0.1
MMM-15 15 127 5 ± 0.1
chain flexibility with temperature will provide passage for the water
MMM-20 20 137 5 ± 0.2 molecules to pass through the matrix due to its lower kinetic diameter
(0.27 nm) in comparison to ethanol (0.43 nm). Consequently, the in-
crease in temperature resulted in higher flux but with decreased se-
to evaluate the water stability of MMMs, the films with highest loading paration factor. Fig. 10 shows a stable increase in total flux by in-
of ZIF-67 (20%) were subjected to water stability test under ambient creasing the temperature. The stable flux for pure PDMS membranes by
conditions. The particles were immersed in water for a period of 7 days increasing the temperature is possibly be due to the bond strength of
up to 21 days 9 (Fig. 8). The stability was characterized by XRD analysis PDMS. The increase in temperature directly influences the bond

54
A. Khan et al. Separation and Purification Technology 206 (2018) 50–58

Fig. 6. SEM images at different modifications of MMMs (a–b: 10 wt%, c–d: 15 wt%, e–f: 20 wt% loading, g: surface image with 20 wt% loading).

strength of PDMS which usually increases with increase in temperature the stable flux for MMMs was also due to the incorporation of thermally
for the polymerization systems. Moreover, PDMS consists of alternating stable ZIF-67 particles which made the overall structure of membranes
silicon atoms which are more stable at higher temperatures. Whereas more stable and in result the increase in total flux was bit stable/

55
A. Khan et al. Separation and Purification Technology 206 (2018) 50–58

Table 3
Density and fractional free volume of the membranes.
Membrane ID Filler Experimental Theoretical Fractional free
loading density (g cm−3)a density volume (FFV)
(%) (g cm−3)

PDMS 0 0.98 ±0 0.98 0.183

ZIF-67 – 0.91 – –
MMM-05 5 0.96 ±0 0.97 0.189
MMM-10 10 0.94 ± 0.01 0.95 0.191
MMM-20 20 0.91 ± 0.01 0.93 0.200

a
At least three samples were used to measure density of the coupons, an
average of the obtained values was reported.

Fig. 7. Membrane uptake with different filler loadings.

Fig. 10. Effect of temperature on total flux as a function of filler loading.

Fig. 8. Water stability of MMMs (20% loading) via XRD patterns.

Fig. 11. Effect of temperature on the separation factor as a function of filler

loading.

Table 4
Activation energies of MMMs.
Membrane ID Filler loading (%) Ej (kJ mol−1)

Pristine PDMS 0 39.6

MMM-05 5 31.6
Fig. 9. Effect of ZIF-67 loadings on total flux and separation factor at 40 °C. MMM-10 10 26.5
MMM-15 15 22.6
MMM-20 20 16.2
gradual not drastic. As an activated process, the effect of temperature
on pervaporation flux can be further described through the Arrhenius
equation: activation energy of ethanol flux. The activation energies of flux cal-
culated from this temperature dependence are presented in Table 4.
−E
J = Joexp ⎛ J ⎞ MMMs have up to 59% lower activation energy and its value is 41% of
⎝ RT ⎠ (8)
that for the pristine membrane. These results support the argument that
where J is the flux, Jo is the pre-exponential factor and Ej is the incorporation of filler provides additional diffusion pathways for the

56
A. Khan et al. Separation and Purification Technology 206 (2018) 50–58

Table 5
Comparative study of PDMS based pervaporation membranes with different fillers for ethanol aqueous solution.
No. Filler Filler loading (wt %) Ethanol content in feed solution (wt%) Feed temperature (°C) Total flux (kg/m2 h) Separation factor Ref.

1 ZIF-71 20 5 50 0.9 9.5 [17]

2 ZIF-71 40 5 50 1.07 10 [21]
3 ZIF-71 40 2 60 NR 12.2 [23]
4 ZIF-71 40 2 60 NR 12.5 [22]
5 ZSM-5 40 5 40 0.4 14 [31]
6 Zeolite-Y 30 6 35 0.09 4.5 [32]
7 Silicalite-1 30 4 50 0.4 15 [33]
8 Silicalite-1 50 5 60 0.4 14.7 [34]
9 ZIF-8 5 5 60 1.2 9.9 [35]
10 MCM-41@ZIF-8 5 5 50 1.2 8.1 [34]
11 MIL-53 40 5 80 5.4 11.1 [35]
12 HF etched ZSM-5 30 5 50 0.8 11 [36]
13 UiO-66/α-Al2O3 a* 10 30 0.6 4.3 [37]
16 UiO-66/α-Al2O3 a* 10 50 1.4 4.9 [37]
17 MAF-6 25 5 40 1.2 14.9 [38]
18 ZIF-67 20 6 40 2.78 15.4 This work

a*: Zr/BDC/H2O/acetic acid/DMF composition of 1:1:1:500:750 NR: Not reported.

permeating molecules leading to less mass transfer resistance, hence Acknowledgements

higher fluxes.
3.4. Comparison with other pervaporation membranes having different
fillers
A comparative analysis of pervaporation studies for the recovery of
ethanol using different fillers is given in Table 5. It is difficult to
compare the performance of these membranes due to different para-
meters, such as type of filler and its crystallinity, filler loading, pre- and
post-treatments of fillers and membranes, methodology of casting the
membrane, thickness of the selective layer etc. Despite all these influ-
ential parameters, the performance was compared on the basis of flux
and separation factor to confirm the behavior of MMMs using different
fillers.
It could be seen that flux and separation factor varied from 0.4 to
5.4 (kg/m2 h) and 4.3–15.4 respectively. Temperature and filler loading
affect the performance of pervaporation membranes up to a certain
level and then it tends to decrease. Similar results could be seen in the
case of MIL-53/PDMS membranes, as reported by Zhang et al. [35].
These MIL-53/PDMS membranes showed higher flux with lower se-
paration factor as compared to other reported studies. The lowest
performance parameters were observed for MMMs consisting of zeolite-
Y due to the strongly hydrophilic nature of this filler. As compared with
other MOF filled membranes, the membranes containing ZIF-67 as filler
in PDMS matrix showed higher flux and separation factor. This could be
attributed to highly hydrophobic nature of these particles and their
high surface area. Therefore, ZIF-67 filled PDMS membranes have great
potential for the recovery of ethanol, and possibly alcohols in general,
from aqueous solutions.
4. Conclusions
ZIF-67 nanoparticles were successfully prepared and PDMS-based
MMMs containing these particles were prepared and characterized. The
advantages of the exceptionally high surface area (1245 m2/g), hydro-
phobicity and pore volume (0.665 cm3/g) of the ZIF-67 nanoparticles as
filler were used for the separation of ethanol/water mixtures, resulting
in a more selective transport of ethanol over water. Filler incorporation
increased the hydrophobicity of the MMMs but lowered the overall
uptake, indicating excellent filler-matrix compatibility. The membranes
with 20% loading of ZIF-67 showed a triple increase in flux and twice in
separation factor for ethanol/water mixtures as compared to unfilled
PDMS membrane. The results obtained are encouraging and may lead
to further application of ZIF-67 containing MMMs for pervaporation or
other membrane processes.
The authors would like to thank Higher Education Commission
(HEC), Pakistan for their grant under NRPU Project # 12837.
References
[1] P. Aptel, et al., Application of the pervaporation process to separate azeotropic
mixtures, J. Membr. Sci. 1 (1976) 271–287.
[2] M. Yasin, et al., Microbial synthesis gas utilization and ways to resolve kinetic and
mass-transfer limitations, Bioresour. Technol. 177 (2015) 361–374.
[3] T.W. Jeffries, R. Schartman, Bioconversion of secondary fiber fines to ethanol using
counter-current enzymatic saccharification and co-fermentation, in: Twentieth
Symposium on Biotechnology for Fuels and Chemicals, 1999. Springer.
[4] A. D-13, Standard Specification for Denatured Fuel Ethanol for Blending with
Gasoline for Use as Automotive Spark-Ignition Engine Fuel, 2013.
[5] L.M. Vane, Separation technologies for the recovery and dehydration of alcohols
from fermentation broths, Biofuels, Bioprod. Biorefin. 2 (6) (2008) 553–588.
[6] A. Jonquières, A. Fane, Filled and unfilled composite GFT PDMS membranes for the
recovery of butanols from dilute aqueous solutions: influence of alcohol polarity, J.
Membr. Sci. 125 (2) (1997) 245–255.
[7] N. Qureshi, M. Meagher, R. Hutkins, Recovery of butanol from model solutions and
fermentation broth using a silicalite/silicone membrane, J. Membr. Sci. 158 (1)
(1999) 115–125.
[8] E. El-Zanati, et al., Modeling and simulation of butanol separation from aqueous
solutions using pervaporation, J. Membr. Sci. 280 (1) (2006) 278–283.
[9] V. García, et al., Pervaporation of dichloromethane from multicomponent aqueous
systems containing n-butanol and sodium chloride, J. Membr. Sci. 326 (1) (2009)
92–102.
[10] C. Yeom, H. Kim, J. Rhim, Removal of trace VOCs from water through PDMS
membranes and analysis of their permeation behaviors, J. Appl. Polym. Sci. 73 (4)
(1999) 601–611.
[11] P.V. Naik, et al., PDMS mixed matrix membranes containing hollow silicalite sphere
for ethanol/water separation by pervaporation, J. Membr. Sci. 502 (2016) 48–56.
[12] G. Liu, et al., Improved performance of PDMS/ceramic composite pervaporation
membranes by ZSM-5 homogeneously dispersed in PDMS via a surface graft/
coating approach, Chem. Eng. J. 174 (2) (2011) 495–503.
[13] M.J.C. Ordoñez, et al., Molecular sieving realized with ZIF-8/Matrimid® mixed-
matrix membranes, J. Membr. Sci. 361 (1) (2010) 28–37.
[14] T. Yang, Y. Xiao, T.-S. Chung, Poly-/metal-benzimidazole nano-composite mem-
branes for hydrogen purification, Energy Environ. Sci. 4 (10) (2011) 4171–4180.
[15] A. Phan, et al., Synthesis, structure, and carbon dioxide capture properties of zeo-
litic imidazolate frameworks, Acc. Chem. Res 43 (1) (2010) 58–67.
[16] Y. Bai, et al., ZIF-8 filled polydimethylsiloxane membranes for pervaporative se-
paration of n-butanol from aqueous solution, Sep. Sci. Technol. 48 (17) (2013)
2531–2539.
[17] Y. Li, et al., ZIF-71 as a potential filler to prepare pervaporation membranes for bio-
alcohol recovery, J. Mater. Chem. A 2 (26) (2014) 10034–10040.
[18] G. Zhang, et al., Enhanced flux of polydimethylsiloxane membrane for ethanol
permselective pervaporation via incorporation of MIL-53 particles, J. Membr. Sci.
492 (2015) 322–330.
[19] S. Basu, et al., Solvent resistant nanofiltration (SRNF) membranes based on metal-
organic frameworks, J. Membr. Sci. 344 (1) (2009) 190–198.
[20] P.V. Naik, et al., PDMS membranes containing ZIF-coated mesoporous silica spheres
for efficient ethanol recovery via pervaporation, J. Mater. Chem. A 4 (33) (2016)
12790–12798.
[21] L.H. Wee, et al., Submicrometer-Sized ZIF-71 filled organophilic membranes for
improved bioethanol recovery: mechanistic insights by Monte Carlo simulation and

57
A. Khan et al.
FTIR spectroscopy, Adv. Funct. Mater. 25 (4) (2015) 516–525.
[22] H. Yin, et al., Free-standing ZIF-71/PDMS nanocomposite membranes for the re-
covery of ethanol and 1-butanol from water through pervaporation, J. Membr. Sci.
529 (2017) 286–292.
[23] H. Yin, et al., Effect of ZIF-71 particle size on free-standing ZIF-71/PDMS composite
membrane performances for ethanol and 1-butanol removal from water through
pervaporation, Ind. Eng. Chem. Res. 56(32) (2017).
[24] N. Wang, et al., MCM-41@ZIF-8/PDMS hybrid membranes with micro- and na-
noscaled hierarchical structure for alcohol permselective pervaporation, Sep. Purif.
Technol. 153 (2015) 146–155.
[25] Y. Pan, et al., Large-scale synthesis of ZIF-67 and highly efficient carbon capture
using a ZIF-67/glycol-2-methylimidazole slurry, Chem. Eng. Sci. 137 (2015)
504–514.
[26] X. Feng, M.A. Carreon, Kinetics of transformation on ZIF-67 crystals, J. Cryst.
Growth 418 (2015) 158–162.
[27] T. Truong, et al., Expanding applications of zeolite imidazolate frameworks in
catalysis: synthesis of quinazolines using ZIF-67 as an efficient heterogeneous cat-
alyst, RSC Adv. 5 (31) (2015) 24769–24776.
[28] R. Gao, et al., Highly efficient polymer–MOF nanocomposite membrane for per-
vaporation separation of water/methanol/MTBE ternary mixture, Chem. Eng. Res.
Des. 117 (2017) 688–697.
[29] H. Zhou, et al., Fabrication of high silicalite-1 content filled PDMS thin composite
pervaporation membrane for the separation of ethanol from aqueous solutions, J.
Membr. Sci. 524 (2017) 1–11.
58
View publication stats
Separation and Purification Technology 206 (2018) 50–58
[30] I.F.J. Vankelecom et al., Parameters influencing zeolite incorporation in PDMS
membranes, J. Phys. Chem. (United States) 98(47) (1994).
[31] G. Liu, et al., Improved performance of PDMS/ceramic composite pervaporation
membranes by ZSM-5 homogeneously dispersed in PDMS via a surface graft/
coating approach, Chem. Eng. J. 174 (2–3) (2011) 495–503.
[32] I.F.J. Vankelecom, et al., Influence of zeolites in PDMS membranes: pervaporation
of water/alcohol mixtures, J. Phys. Chem. 99 (35) (1995) 13193–13197.
[33] A. Yadav, et al., Nanocomposite silicalite-1/polydimethylsiloxane membranes for
pervaporation of ethanol from dilute aqueous solutions, Ind. Eng. Chem. Res. 52
(14) (2013) 5207–5212.
[34] N. Wang, et al., Tuning properties of silicalite-1 for enhanced ethanol/water per-
vaporation separation in its PDMS hybrid membrane, Micropor. Mesopor. Mater.
201 (2015) 35–42.
[35] H. Yan, et al., Sonication-enhanced in situ assembly of organic/inorganic hybrid
membranes: evolution of nanoparticle distribution and pervaporation performance,
J. Membr. Sci. 481 (2015) 94–105.
[36] Z. Xia, et al., Mixed matrix membranes with HF acid etched ZSM-5 for ethanol/
water separation: preparation and pervaporation performance, Appl. Surf. Sci. 259
(41) (2012) 547–556.
[37] M. Miyamoto, et al., An Organoselective Zr‐Based Metal Organic Framework
UiO‐66 Membrane for Pervaporation, Eur J Inorg Chem 2017(14) (2017).
[38] Q. Li, et al., Improved ethanol recovery through mixed-matrix membrane with
hydrophobic MAF-6 as filler, Sep. Purif. Technol. 178 (2017) 105–112.