Journal of Membrane Science 354 (2010) 4854

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Journal of Membrane Science

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

Zeolitic imidazolate framework ZIF-7 based molecular sieve membrane for

hydrogen separation
Yanshuo Li a,b, , Fangyi Liang a , Helge Bux a , Weishen Yang b , Jrgen Caro a
a

Institute of Physical Chemistry and Electrochemistry, and the Laboratory for Nano and Quantum Engineering (LNQE) in Cooperation with
the Center for Solid State Research and New Materials, Leibniz University Hannover, Hannover 30167, Germany
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China

a r t i c l e

i n f o

Article history:
Received 2 December 2009
Received in revised form 9 February 2010
Accepted 27 February 2010
Available online 6 March 2010
Keywords:
Metalorganic frameworks
Zeolitic imidazolate frameworks
Molecular sieve membranes
ZIF-7
Gas separation

a b s t r a c t
Hydrogen-based energy system could address issues related to global climate change, energy security,
and local air pollution. Thermally and hydrothermally stable microporous membranes with intrinsic high
H2 /CO2 selectivity are highly demanded. A novel zeolitic imidazolate framework (ZIF-7) membrane was
tested for its gas separation performance. ZIFs are microporous materials and belong to the new class of
metalorganic frameworks (MOFs). ZIF-7 is formed by bridging benzimidazolate anions and zinc cations
resulting in a sodalite (SOD) topology with a pore size of about 0.3 nm. The ZIF-7 membrane exhibited
promising H2 separation abilities. At 220 C, the H2 permeance is 4.5 108 mol m2 s1 Pa1 and the
mixture separation factors for H2 /CO2 , H2 /N2 , and H2 /CH4 are 13.6, 18.0, and 14.0, respectively. As a result
of molecular sieving mechanism, the ideal selectivities and mixture separation factors are identical. The
permeation of H2 through the ZIF-7 membrane is highly activated with an apparent activation energy of
11.9 kJ mol1 . Due to the ultra-hydrophobic properties of ZIF materials, the ZIF-7 membrane also showed
excellent hydrothermal stability in the presence of steam. Our results clearly demonstrate that ZIF-7
membranes have an intrinsic high H2 /CO2 selectivity and a promising application in hydrogen separation,
which is based on its very narrow and well-dened crystal pore structure.
2010 Elsevier B.V. All rights reserved.

1. Introduction
Hydrogen-based energy system could address issues related
to global climate change, energy security, and local air pollution,
which inspires the enormous research efforts on hydrogen production, separation, purication, and storage in the industrial and
academic elds [1]. At present, large-scale hydrogen production
generally occurs via steam reforming followed by water-gas shift
(WGS). The product contains primarily H2 and CO2 [2]. H2 selective membranes, which provide an attractive alternative to PSA
and cryogenic distillation, can be of great benet for both the
cost-effective H2 purication and the increase of the H2 yield in
a WGS membrane reactor by driving the chemical equilibrium
[35]. H2 -permselective inorganic membranes, due to their high
thermal resistance and mechanical strength, have the potential to
work directly with the WGS reactions at high temperature and
high pressure [6,7]. Dense Pd-based metallic membranes, carbon
molecular sieve (CMS) membranes, microporous amorphous silica or doped silica membranes, and zeolite membranes are in the

Corresponding author. Tel.: +86 411 4379137; fax: +86 411 84694447.
E-mail addresses: yanshuo.li@pci.uni-hannover.de (Y. Li),
Juergen.caro@pci.uni-hannover.de (J. Caro).
0376-7388/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.memsci.2010.02.074

focus of current research in development of inorganic membranes

for H2 separation. The Pd-based membranes possess theoretically
innite H2 selectivity and reasonable permeance at high temperature (>500 C) but suffer from rapid membrane degradation when
they are in contact with CO or H2 S even at ppm-levels [4,8]. The
high Pd cost is another major barrier for Pd-based membranes.
CMS membranes have been found to have exceptional H2 separation properties with high-purity feeds, however, they are very
brittle and fragile and difcult to be prepared as thin supported
membranes [9]. The microporous amorphous silica membranes,
especially the ones fabricated by chemical vapor deposition (CVD)
methods, are able to provide excellent H2 selectivity over small
molecule gases but have serious issues with material instability in
humid conditions [7]. Highly siliceous microporous zeolite membranes, such as MFI, DDR and SAPO-34 types, possess excellent
hydrothermal stability and chemical resistance but showed low
H2 /CO2 separation factors, due to the existence of intercrystalline
micro defects and the relatively large zeolitic pores compared
with the small and very close kinetic diameters of H2 and CO2
(0.289 and 0.330 nm, respectively). Normally post-treatment modication and pore size engineering are necessary to improve the
H2 /CO2 separation factors of these microporous zeolite membranes [1012]. Therefore, thermally and hydrothermally stable
microporous membranes with intrinsic high H2 /CO2 selectivity are

Y. Li et al. / Journal of Membrane Science 354 (2010) 4854

highly demanded with regards to the applications in WGS process.

Zeolitic imidazolate frameworks (ZIFs), a sub-family of metalorganic frameworks (MOFs), consist of transition metal ions (Zn2+ ,
Co2+ ) and imidazolate linkers which form 3D tetrahedral frameworks frequently resembling zeolite topologies with pore apertures
from 0.2 to 1.5 nm [13]. Different to their MOF analogues with
carboxyl-ligands, a number of ZIFs exhibit exceptional thermal,
hydrothermal and chemical stability. All these properties make ZIFs
excellent candidates for their use in the construction of molecular
sieve membranes with superior performances. ZIFs with sodalite
(SOD) topology, such as ZIF-7, ZIF-8, ZIF-9, and ZIF-90 [14], are of
particular interests for membrane applications, due to their monomodal pore size distributions and special diffusion pathways for
guest molecules, i.e. large sodalite cages interconnected by small
six-membered rings [1316], resulting in an uncoupled ux of the
molecular components in a mixture separation [17].
Recently, we successfully prepared a titania-supported ZIF-8
(cubic symmetry, SOD topology) membrane through microwaveassisted in situ crystallization [18]. The ZIF-8 membrane showed a
H2 /CH4 separation factor higher than 10 but a relative low H2 /CO2
separation factor of 4.5 (approximate to that of Knudsen selectivity), which can be attributed to the very exible and slightly larger
pore size of ZIF-8 (0.34 nm) compared with the kinetic diameter of
CO2 molecules (0.33 nm).
ZIF-7 possesses an open-framework structure with SOD topology in hexagonal symmetry, formed by bridging benzimidazolate
(bim) anions and zinc cations [16]. The pore size of ZIF-7 is about
0.3 nm, which is just in between the size of H2 (0.29 nm) and CO2
(0.33 nm). Therefore, ZIF-7 membranes are expected to achieve a
high selectivity of H2 over CO2 through molecular sieving effect,
which has been successfully proved by our recent study [23]. A
compact ZIF-7 thin layer was synthesized onto a porous alumina
support using microwave-assisted secondary growth. In gas permeation tests, the ZIF-7 membrane showed a clear cut-off between
H2 and CO2 , with a H2 /CO2 separation factor of 6.5, showing that a
ZIF-7 membrane is very promising for hydrogen separation.
In the present work, aiming at the potential applications in
hydrogen purication and recycling and integrating ZIF-7 membranes into the WGS process, a detailed investigation on both single
and binary gas permeations through the ZIF-7 membrane was performed, including He, H2 , CO2 , N2 CH4 , and their binary mixtures.
The inuences of operating parameters such as permeation temperatures, feed compositions, and the co-existence of steam on the
separation of H2 /CO2 binary mixtures were systematically studied.
2. Experimental
2.1. Membrane preparation
ZIF-7 membranes were prepared according to our reported
method with minor alterations [23]. Briey, an asymmetric alumina discs (Inocermic, Hermsdorf Institute of Technical Ceramics)
was rstly surface seeded with the ZIF-7 nano seeds by dip-coating
with an aqueous seeding sol which contained ca. 4 wt.% ZIF-7 nano
seeds and 2.5 wt.% polyethyleneimine (PEI). After that, microwaveassisted secondary growth was carried out to crystallize a compact
ZIF-7 layer on the support. In a typical procedure, 20 mL N,Ndimethylfomamide (DMF) was added into a solid mixture of 0.38 g
Zn(NO3 )2 6H2 O and 0.20 g Benzimidazole (bim) with stirring. This
clear solution was transferred into a Teon autoclave in which a
seeded support was placed vertically. Afterwards the autoclave was
heated in a microwave oven (Ethos 1, MLS, using a maximum power
of 300 W) to 100 C in 10 min, and kept at 100 C for 2.5 h. After cooling down, the membrane was washed with methanol and dried at
50 C over night.

49

2.2. Characterizations
The XRD measurements were carried out in reection mode
on Philips-PW1710 diffractometer equipped with a secondary
graphite monochromator with CuK radiation (wavelengths
 = 0.154 nm). Data were collected in a step-scan mode in the range
of 545 with step-width of 0.1 and interval time of 1 s.
The SEM images were performed on a JEOL JSM-6700F instrument at an accelerating voltage of 2 kV, a 10 A current and a
working distance of 815 mm. For cross-sectional SEM pictures,
the membrane was rst simply broken and cleaned in an air ow
to remove dust. The membrane fragment was then coated with a
nanometer scale gold layer to reduce charging effects.

2.3. Gas permeation experiments

The as-synthesized ZIF-7 membrane disk was sealed into a
stainless steel permeation cell using VITONTM gaskets. Permeation temperatures of the cell were controlled by a temperature
controller with a heating tape. Before gas permeation tests, the
as-synthesized ZIF-7 membrane was activated at 200 C sweeping
with N2 for more than 24 h to remove the occluded water molecules
in the ZIF-7 channels.
In this work, except for the single gas permeation of He and
that of H2 for comparison purpose, which were measured using
soap-lm method, all the measurements were performed using the
WickeKallenbach technique with an on-line gas chromatography
(HP 6890).
For the single gas measurements, the feed ow rates were set to
50 ml min1 . The pressures at both sides were constant at 1 bar. For
all measurements N2 was used as sweep gas, except for the N2 permeation measurement where CH4 was used as sweep gas. For the
mixed gas measurements feed ow rate was constant with a total
volumetric ow rate of 100 ml min1 with each gas of 50 ml min1
(1:1 mixture). The pressures at the feed sides and permeate side
were both constant at 1 bar. N2 was used as sweep gas, except for
the H2 /N2 measurement where CH4 was used as sweep gas. The
sweep ow rates were set to 50 ml min1 in all experiments.
For all the measurements, the stage cut, that is, the ratio of permeate to feed ow rate, was always very low (below 1%). Under
these conditions, the residue composition is essentially equal to
the feed composition.
To test the hydrothermal stability of the membrane, an equimolar H2 /CO2 mixed gas with total ow rate of 100 ml min1 and
pressure of 1 bar bubbled through a water saturator at room temperature (25 C) before entering the permeation cell. The steam
concentration in this feed is around 3 mol%.
The membrane permeance, Fi , is dened as:
Fi =

Ni
Pi A

where Ni is the permeate rate of component i (mol s1 ), Pi the

transmembrane pressure difference of i (Pa), and A is the membrane
area (m2 ).
The ideal selectivity (permselectivity) is calculated as the ratio
of single gas permeances.
For the calculation of the H2 mixture separation factor, H2 ,j ,
we assumed that the ow rate through the membrane is negligible
compared to the feed ow rate and the sweep ow rate and therefore the concentration of a component in the retentate is nearly the
same as in the feed:
H2 ,j =

yH2 /yj
xH2 /xj

50

Y. Li et al. / Journal of Membrane Science 354 (2010) 4854

where x is the molar fraction in the retentate, y is the mole fraction

in the permeate, j represents CO2 , N2 or CH4 .
The apparent activation energy, Eact , is analyzed according to
the Arrhenius equation:

 E 
act

Fi = Fi0 exp

RT

where Fi is the permeance of component i, Fi0 the pre-exponential

factor, R the ideal gas constant (8.314 J mol1 K1 ), and T the temperature in Kelvin (K). A plot of ln (Fi ) versus T1 gives a straight
line, whose slope is used to determine Eact .
3. Results and discussions
3.1. Characterization of the ZIF-7 membrane
The crystal phase of the as-synthesized ZIF-7 membrane was
identied by X-ray diffraction (XRD). Compared with the reported
structural data [13,16], it can be found in Fig. 1a that the membrane
is composed of pure ZIF-7 and free of ZnO as impurity phase. The
XRD pattern of the ZIF-7 membrane also shows that the ZIF-7 layer
has no preferential orientation.
The morphologies of the as-synthesized ZIF-7 membranes were
observed using scanning electron microscope (SEM). The SEM topview (Fig. 1b) shows that the ZIF-7 layer consists of randomly
oriented grains, which coincides with the XRD result. The ZIF-7
grains are 12 m and well intergrown. The SEM cross-sectional
view (Fig. 1c) shows that the ZIF-7 top layer is about 2 m thick.
Compared with other MOF membranes [1822], the ZIF-7 mem-

Fig. 2. Single and mixed gas (from equimolar binary mixtures) permeances of the
ZIF-7 membrane at 220 C as a function of molecular kinetic diameters.

brane synthesized in the current work is much thinner, which is

essential for achieving high permeances.
3.2. Gas separation performance of the ZIF-7 membrane
The ZIF-7 membrane was tested after activation in single gas and
binary mixtures permeations at 220 C. Fig. 2 (also see Table 1) gives
the permeances of H2 , CO2 , N2 , and CH4 as single gases as well as
from their equimolar binary mixtures through the ZIF-7 membrane
as a function of the kinetic diameter of the gas molecules. Compared with our former report [23], the ZIF-7 membrane measured
in this study showed improved H2 selectivities along with slightly

Fig. 1. (a) XRD pattern, (b) SEM Top view, and (c) SEM cross-sectional view of the ZIF-7 membrane.

Y. Li et al. / Journal of Membrane Science 354 (2010) 4854

51

Table 1
Permeances, H2 ideal selectivities and H2 mixture separation factors from equimolar binary mixtures at 220 C.
Permeance (108 mol m2 s1 Pa1 )
WickeKallenbach method using gas chromatography
Single gas
4.55
H2
0.35
CO2
0.22
N2
0.31
CH4
Mixed gas
H2 (50 vol.% in CO2 )
CO2 (50 vol.% in H2 )
H2 (50 vol.% in N2 )
N2 (50 vol.% in H2 )
H2 (50 vol.% in CH4 )
CH4 (50 vol.% in H2 )
Soap-lm method
Single gas
He
H2

H2 ideal selectivity

13.0
20.7
14.7

4.55
0.33
4.42
0.25
4.36
0.31

4.07
2.92

decreased permeances. For both single and binary gas permeation,

there is a clear cut-off between H2 and CO2 . The H2 /CO2 ideal selectivity and separation factor are 13.0 and 13.6, respectively, which
exceed remarkably the Knudsen separation factor (4.7). For the
1:1 binary mixtures, the H2 /N2 and H2 /CH4 separation factors are
18.0 and 14.0, respectively, both are higher than the corresponding
Knudsen separation factors (3.7 and 2.8, respectively). In addition, it is notable that the permeance order of He (4.00 a.u.) and
H2 (2.01 a.u.) followed molecular size rather than mass (Table 1),
which can be seen as an indication of high quality microporous
membranes [26]. Since CO2 , N2 and CH4 are all size-excluded from
the internal pores of ZIF-7, these large molecules have no hindering
effects upon the diffusion of H2 through the ZIF-7 membrane, which
is reected by Fig. 2 showing that the permeances are almost the
same for H2 as single gases (4.55 108 mol m2 s1 Pa1 ) and H2
in the 1:1 binary mixtures (4.364.55 108 mol m2 s1 Pa1 ). In
case of zeolite membranes, however, deviations between the mixture separation factor and the ideal selectivity are often observed.
For example, the mixture separation factor of an AlPO4 membrane for the H2 /CO2 binary systems was 9.7, much lower than the
ideal selectivity of 23.9 derived from the single-component systems [24]. The H2 /CO2 separation factor (10.8) of a CVD modied
ZSM-5 membrane was also lower than the ideal selectivity (17.5)
even at 450 C [10]. The non-zero permeances of CO2 , N2 and CH4
can be attributed to a certain inuence of the non-size selective
mass transport through the imperfect sealing or through the grain
boundaries of the polycrystalline ZIF-7 layer. This non-size selective
Knudsen-like mass transport also accounts for the slightly higher
permeance of CH4 (16.04 a.u.) than that of N2 (28.01 a.u.), although
the former is more bulky.
Fig. 3 compares the separation performance of our ZIF-7 membrane with literature reports on microporous inorganic membranes
regarding H2 /CO2 separation. Here, only the data of H2 /CO2 selectivities higher than the Knudsen selectivity (4.7) are collected. The
upper bound of polymeric membranes in the selectivity vs. permeance plot is derived from the latest Robesons tradeoff line [25].
The most direct observation is that the performances of the microporous inorganic membranes are much higher than those of the
polymeric ones, which can mainly be attributed to their precise
size-selective molecular sieving abilities. The data points above the
dashed lines in the upper zone, corresponding to high selectivities,
are all derived from single gas permeation tests, i.e. ideal selectivities [2630]. However, interplays between permeates (correlation
effects) are generally not negligible, which can result in a prominent
deviation of the mixture separation factor from the ideal selectivity

H2 separation factor

13.6
18.0
14.0

0.72

[10,24]. The dashed line represents as a guide for the eyes the upper
bound for mixture permeation results obtained on H2 /CO2 binary
mixtures (i.e. mixture separation factors) (Fig. 3).
In the scope of our retrieval, the solgel derived silica membranes exhibit reasonable selectivities of several tens but low
permeances (<108 mol m2 s1 Pa1 ) [31,32], likely due to the
multiple dip-coating process which is essential to eliminate the
large defects in the separating layers. The silica-based membranes
prepared by CVD exhibit higher ideal selectivities (up to 1000)
and comparable permeances (107 mol m2 s1 Pa1 at high temperature) [26,27,30], whereas the separation performance toward
mixed gases was not so distinctive, showing H2 /CO2 separation
factors of about 10 [33]. In addition, the fabrication of these membranes is complicated, normally several intermediate layers graded
in size are needed to guarantee reasonable permeances. The zeolite membranes exhibit high permeances (107 mol m2 s1 Pa1 )
but relatively low selectivities (10). Only two types of zeolite
membranes (AlPO4 [24] and P/NaX [34]) are reported to have
intrinsic H2 /CO2 separation factors much beyond Knudsen selectivity. But both membranes showed decreased separation factors
with temperature. By surface modications, Al-ZSM-5 [10], B-ZSM5 [11], and DDR [12] membranes, which originally showed CO2
selectivities especially at low temperatures due to the preferen-

Fig. 3. H2 /CO2 mixture separation factor and ideal selectivity vs. H2 permeance for
microporous inorganic membranes. (The dashed line represents the upper bound
of the mixture separation factor for microporous inorganic membranes. Note that
only the data of the ideal selectivity are above the dashed line. The upper bound line
for polymeric membranes is drawn based on Ref. [25] by conversing permeability
to permeance assuming a membrane thickness of 50 m. The literature data are
divided into three groups according to the permeation temperatures. The numbers
beside the symbols are the corresponding reference numbers.)

52

Y. Li et al. / Journal of Membrane Science 354 (2010) 4854

tial adsorption of CO2 at the non-zeolitic defects or the internal

zeolitic channels, can be reversed into H2 -selective membranes.
The modication is intent to eliminate the defects and to reduce the
effective pore diameters by selectively cracking of silane molecules,
such as methyldiethoxysilane (MDES) [10,11] or tetraethylorthosilicate (TEOS) [12], at the defects or pore entrances of the zeolites. To
avoid excessive silica deposition, on-steam counter diffusing CVD
techniques was used [10]. Although controlled CVD modication
of zeolite membranes provides a way to achieve high H2 /CO2 separation performance, the processability in a large-scale is still a big
challenge. As for MOF membranes, the reported H2 /CO2 separation
factors so far are generally lower than the Knudsen selectivity. A
copper net supported HKUST-1 membrane was reported to exhibit
H2 /CO2 separation factor of 6.5 at room temperature, but the separation factor decreased to 4 with slight increase of temperature to
75 C [35].
The ZIF-7 membrane prepared in the present work possesses
a good balance between H2 permeance and selectivity. The performance of the as-synthesized ZIF-7 membrane without any
post-treatment is already close to the upper bound (dashed line)
of microporous inorganic membranes. Moreover, the ZIF-7 membrane is thermally stable enough to be used at elevated temperature
(stable at least to 500 C in air according to the TG analysis, see
[23]). Extrapolated to a temperature of 450 C (see Section 3.3), the
expected permeance of H2 is of the order 107 mol m2 s1 Pa1
and the corresponding H2 /CO2 separation factor higher than 30.
These values would be superior to the performance of up-to-date
microporous inorganic membranes. Efforts are currently under way
to solve the sealing problems to perform separation measurements
at high temperatures. Meanwhile, it became possible to further
improve the performance of the ZIF-7 membranes by eliminating the non-size selective pathways and reducing the membrane
thickness through synthesis optimization.
3.3. Effect of temperature on H2 /CO2 separation through the
ZIF-7 membranes
Fig. 4 represents the variation of the H2 and the CO2 permeances
and the corresponding separation factors from their equimolar
binary mixture in the temperature range of 50220 C. The permeance of H2 decreases quickly with decreasing temperature
indicating an activated diffusion process. The apparent activation
energy (Eact ) for H2 diffusion is obtained by tting the experimental gas permeance data (160220 C, in this range measurement
accuracy is better than 2%) to an Arrhenius equation. The calculated Eact for H2 is 11.9 kJ mol1 . As pointed out by Burggraaf and
co-workers, the activation energy for H2 permeance gives a good
correlation with the separation factor and can be used as a mea-

Fig. 4. H2 and CO2 permeances from equimolar binary mixtures and H2 /CO2 mixture
separation factors of the ZIF-7 membrane as a function of increasing and decreasing
temperature.

sure of membrane quality [38]. Our experimental result supports

the opinion that high quality membranes should have an activation energy of at least 10 kJ mol1 for H2 permeance. The Eact of
H2 on our ZIF-7 membrane is in good agreement with the values
measured on other high-performance microporous membranes for
the H2 /CO2 separation. As examples, CVD modied silica membrane (ideal selectivity = 1000 at 600 C, Eact = 14.9 kJ mol1 ) [26],
CVI (chemical vapor inltration) modied silica membrane (ideal
selectivity = 32 at 200 C, Eact = 15.8 kJ mol1 ) [36], SiC membrane
(separation factor = 50 at 200 C, Eact = 12 kJ mol1 ) [37], and CVD
modied DDR zeolite membrane (ideal selectivity = 5.9 at 500 C,
Eact = 9.62 kJ mol1 ) [12].
In the entire tested temperature range, the permeance of
CO2 is almost constant (0.3 108 mol m2 s1 Pa1 ). Due to the
increase of the H2 permeance with temperature, the H2 /CO2 separation factor increases remarkably from 5.4 at 50 C to 13.6 at
220 C. A further improvement of both the H2 permeance and the
H2 /CO2 separation factor can be predicted for temperatures higher
than 220 C, as already discussed in Section 3.2.
Furthermore, it is worth noting that the ZIF-7 membrane
showed a very good reversibility upon temperature cycling (Fig. 4).
The permeances measured during the heating-up stage are consistent very well with that during the cooling-down stage. This
temperature reversibility of the permeance combined with its high
thermal stability recommends the ZIF-7 membrane for the high
temperature H2 separation.
3.4. Effect of H2 concentration in the feed on H2 permeance in the
H2 /CO2 separation through the ZIF-7 membranes
To evaluate the inuence of the feed composition on the molecular sieving of hydrogen, the separation of H2 /CO2 gas mixture was
studied at 220 C for different H2 concentrations in the feed at a
total feed pressure of 1 bar (Fig. 5). Both the H2 and the CO2 permeances are nearly unchanged in the entire test range. The H2 /CO2
separation factor, consequently, is nearly constant irrelative to H2
fraction in the feed. This nding can be well interpreted by the
size-exclusive molecular sieving mechanism. Firstly, as has been
discussed in Section 3.2, only H2 molecules will enter the ZIF-7
pores and permeate. Secondly, external surface diffusion (i.e., F2.J in
the model of gas transport in zeolite crystal membranes proposed
by Barrer [39]) is not rate determining with regard to activated
transport process, e.g. the case in ZIF-7 membrane [40], thus the
inuence of competitive adsorption of CO2 molecules on the exter-

Fig. 5. H2 and CO2 permeances from equimolar binary mixtures, and H2 /CO2
mixture separation factors of the ZIF-7 membrane at 220 C for different H2 concentrations in the feed.

Y. Li et al. / Journal of Membrane Science 354 (2010) 4854

53

4. Conclusion

Fig. 6. Hydrothermal stability test of the ZIF-7 membrane in the separation of an

equimolar H2 /CO2 mixture with adding of 3 mol% steam at 220 C. Dry feed: empty
symbols; wet feed: lled symbols.

nal surface of the ZIF-7 membrane is negligible, especially at high

temperature like 220 C as in the current studies. Furthermore,
under our test conditions (220 C and partial pressure of H2 from 0.1
to 0.9 bar), the adsorption isotherms of H2 on ZIF-7 can be assumed
to obey Henrys law, therefore, the permeance of H2 is independent
of its partial pressure difference.
This observation is different from other reports regarding
H2 /CO2 binary mixtures. For example, at 450 C and a total feed
pressure of 1 bar, Dong et al. reported that the H2 permeance was
directly proportional to the H2 fraction in the feed on the CVD modied ZSM-5 membrane [10]. They attributed this observation to the
counter permeation of sweep gas He. On the contrary, a dramatic
decrease of the H2 permeance with decreasing the H2 fraction in
the feed was reported on a carbon membrane at room temperature
[41]. The H2 permeance became zero at H2 molar fraction below
0.3 with a total pressure at the feed side of 1 bar. Pore blocking by
CO2 adsorption on the membrane surface was regard as the cause
of this abnormal phenomenon.
3.5. Hydrothermal stability of ZIF-7 membranes
The limited hydrothermal stability of amorphous microporous
membranes, e.g. silica membranes, will exclude their use for H2
removal in the presence of steam. To test its hydrothermal stability, the ZIF-7 membrane was exposed to an equimolar H2 /CO2 feed
containing 3 mol% steam at 220 C. The ZIF-7 membrane showed a
very good stability of more than 50 h as shown in Fig. 6. Adding of
steam to the feed causes a slight decrease of the H2 permeance by
2% compared with the dry feed. The H2 permeance can be restored
after switching off the steam. This complete reversibility indicates
a mutual mixture permeation effect rather than a structural damage. The small reduction of the H2 permeance, therefore, can be
attributed to the parallel permeation of H2 O and H2 through the
ZIF-7 membrane, since the kinetic diameter of H2 O (0.26 nm) is
smaller than the pore size of ZIF-7. A slight increase of 10% the
permeances of H2 and CO2 during the stability test was observed,
and accordingly the separation factor is unchanged, indicating an
improvement of the membrane performance. This nding can be
explained by taking into consideration the support inuence. Some
residual PEI components in the support from the seeding procedure might be removed by the permeation of H2 O, resulting in
a reduced support resistance and increased permeance. For comparison, Oyama et al. reported that the H2 permeance of a pure
silica membrane declined by more than 80% when contacted with
16 mol% steam at 600 C for 10 h [31].

Metalorganic frameworks, as a newly developed family of

crystalline microporous materials, have attracted numerous interests of membranologists, especially those working on microporous
membranes. To be used as membrane materials, their stabilities,
including thermal, hydrothermal and chemical stabilities should
be carefully considered. In the current work, a novel zeolitic imidazolate framework ZIF-7 membrane was tested for H2 separation
at elevated temperatures. Besides a reasonable performance for
H2 /CO2 separation, the ZIF-7 membranes showed good thermal and
hydrothermal stabilities. This study demonstrates that MOF materials, especially ZIFs, are promising candidates for constructing
gas separation membranes. Due to its broad temperature window
and feed concentration window, the ZIF-7 membrane seems to
be promising for both hydrogen production and recycling. Using
the ZIF-7 membrane to build a WGS membrane reactor is also
intriguing. To this end, permeation tests at actual WGS reaction
pressure (ca. 1530 bar) are essential. Towards a comprehensive
understanding of the gas transport through ZIF-7 membranes, gas
sorption experiments are demanded.
Acknowledgments
Y.-S. Li is grateful for the nancial support from the Alexander von Humboldt Foundation. DFG Priority Program 1362 Porous
Metal-Organic Frameworks is thanked for nancial support.
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