Results in Engineering 15 (2022) 100609

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Results in Engineering
journal homepage: www.sciencedirect.com/journal/results-in-engineering

Manipulation strategies for improving gas separation performance on

metal-organic frameworks membranes
Haiqian Lian a, Bin Bao a, Jinfeng Chen b, Wenhe Yang a, Yu Yang a, Rujing Hou a, Shengui Ju a, **,
Yichang Pan a, *
a
State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing, 210009, PR China
b
School of Environmental Science and Engineering, Nanjing Tech University, Nanjing 210009, PR China

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

Keywords: Metal-organic frameworks (MOFs) membrane is a research hotspot for gas separation due to their high variety
Metal-organic frameworks and adjustability in structure and function. In recent years, despite some achievements gained for the supported
Gas separation MOF polycrystalline membranes through in-situ design and synthesis, the low gas separation performance re­
Polycrystalline membranes
mains the challenge for their further gas separation applications. Therefore, this review summarizes the
Manipulation strategies
manipulation strategies to improve the gas separation performance of MOF membranes. Particular attention is
paid to aperture/cage modification, defects elimination, membranes thickness control, crystal orientation
adjustment, and surface modification of support layer at the microscopic/mesoscopic level to illustrate their
effect on improving MOF membrane selectivity, permeance, and long-term stability. Moreover, some possible
opportunities and challenges for further development in the field of gas separation are also provided at the end of
this review.

1. Introduction
The separation process accounts for about 50% of the total energy
consumption in the chemical industry [1]. Membrane-based separation
technology stands out among the traditional techniques such as distil­
lation [2], adsorption [3], and absorption [4], due to the advantages of
high energy efficiency, and small physical and chemical footprints
(Fig. 1a) [5–7]. Even though there are a handful of the current
market-dominated polymeric membrane materials for gas separation
[8], the issues of permeability/selectivity trade-off, plasticization, and
poor physical and chemical stability, severely hinder their further
scale-up application in the industry [9,10]. Although the great progress
made in the past ten years, polymeric membrane has yet achieved the
ideal gas separation performance, that is, reliable stability, high selec­
tivity, and the concurrent high permeability [11].
Metal-organic frameworks (MOFs) are a new type of porous crys­
talline materials composed of metal ions or atomic clusters and organic
ligands [12,13]. The diversity of structures and pore sizes make MOFs an
attractive advanced separation medium [14]. The supported MOF
polycrystalline membranes show their great potential for mixed gas
separation at a manner of high energy efficiency [15]. The uniform pore
size and high porosity can realize sharp molecular sieving and fast gas
transportation. Hence, it breaks the permeance/selectivity trade-off and
provides MOF membrane with both high selectivity and high permeance
[16]. A continuous MOF-5 membrane was successfully prepared by Lai
and Jeong et al. through the in-situ growth method and applied to gas
separation for the first time [17]. Subsequently, various MOF membrane
materials (IRMOFs, HKUST-1, MILs, UiOs, ZIFs) have been extensively
examined in the field of gas separation (Fig. 1b). Numerous synthesis
methods for MOF membranes have also been developed [11,18,19].
Hence, MOF membranes have been widely fabricated for CO2 capture,
H2 purification, and hydrocarbon separation, and show superior sepa­
ration performance to those of state-of-the-art conventional polymeric
membranes [14,20–22]. However, the challenges of defects control,
membrane brittleness, poor reproducibility, and long-term stability
remain and dramatically slow down the industrialization roadmap of
MOF membranes [21]. To meet these challenges, a large number of
reviews have been reported, but they mainly focus on preparation
methods and microstructural regulation [12–14]. Especially, the rela­
tionship between the microstructure of MOF membrane and its

* Corresponding author.
** Corresponding author.
E-mail addresses: jushengui@njtech.edu.cn (S. Ju), panyc@njtech.edu.cn (Y. Pan).

https://doi.org/10.1016/j.rineng.2022.100609
Received 11 May 2022; Received in revised form 28 June 2022; Accepted 22 August 2022
Available online 27 August 2022
2590-1230/© 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
H. Lian et al. Results in Engineering 15 (2022) 100609

corresponding gas separation performance is rarely reviewed. From the

viewpoint of MOF membrane performance, a higher membrane selec­
tivity has the potential to lower the whole system energy consumption
[23]; a higher membrane permeance is related to a lower membrane cost
[24]; and a sufficiently robust membrane is with a potentially granted
high economic efficiency [25]. Therefore, manipulation strategies to
achieve MOF membrane with the aforementioned performance and
properties are of significant importance to advancing MOF membrane
for practical application [14,26].
In this review, we systematically summarize the manipulation stra­
tegies and the recent research progress for MOF membranes application
to gas separation. Particular attention was paid to aperture/cage
modification and defects elimination to improve membrane selectivity;
membrane thickness reduction and crystal orientation regulation to
improve gas permeance; and support layer surface modification to
improve membrane stability (Fig. 2). The relationship between MOF
membrane structure properties and their corresponding gas separation
performance illustrated in this review would give readers of interest a
better understanding of structure—property relationships in MOFs. The
opportunities and challenges for MOF membranes in the field of gas
separation are also highlighted at the end of this work.

2. Manipulation strategies for selectivity

Gas selectivity has the key responsibility for the final product purity
and whole system energy consumption. This section highlights several
main factors that significantly affect MOF membrane selectivity per­
formance including the aperture size adjustment, cage functional
modification, and defect elimination. The separation performance of
MOF membrane corresponding to typical manipulation strategies for
selectivity is summarized in Table 1.
2.1. Aperture size adjustment
Porous MOF materials show great application prospects in the field
of gas separation due to their highly tunable aperture size. For supported
MOF polycrystalline membranes, the aperture size can be adjusted
through metal ion doping [27], ligand doping [28], and framework
flexibility control [29] for specific separation systems.
2.1.1. Metal ion doping
The metal ions doping will allow two different metal ions to be
incorporated into a MOF framework. The newly introduced metal ions
Fig. 2. Schematic diagram of manipulation strategies for improving gas sepa­
ration performance on MOF membranes.
coordinated with ligands can effectively regulate aperture size in MOF
micro-structure achieved by the length control of the generated coor­
dination bond [27]. Usually, a longer coordination bond contributes to
the enlarged aperture size associated with enhanced gas flux. A shorter
bond leads to the narrowed aperture size accompanying by improved
separation factor. Therefore, the new MOF framework provides addi­
tional functionality while maintaining the original functionality. For
example, Eddaoudi et al. [30] partially replaced Zn2+ (longer coordi­
nation bond) in the SIFSIX-3-Zn framework by Cu2+ (shorter coordina­
tion bond), resulted in the reduced aperture size (from 3.84 to 3.5 Å)
which in turn increased the charge density around the adsorbed CO2,
fastened its adsorption kinetics, and hence, increased CO2 uptake
(10–15 times). Yang et al. [31] also prepared ZIF-108 crystals containing
two metals by partially replacing Zn2+ in the ZIF-108 framework with
Co2+. The longer Co–N bonds than Zn–N resulting from the larger ionic
radius of cobalt than that of zinc led to the enlarged aperture size.
Similarly, a dense CuBTC/MIL-100 membrane was synthesized by

Fig. 1. (a) Relative energy consumption of all types of separation technologies in the industry. Reproduced with permission from Ref. [11]. Copyright 2021 Elsevier
B.V. (b) Research development of gas separation MOF membranes between the years 2009–2021. Retrieved from the Web of Science on March 25th, 2022.

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H. Lian et al. Results in Engineering 15 (2022) 100609

Table 1
Separation performance of MOF membranes and corresponding typical manipulation strategies.
Manipulation Strategies Membrane Preferred Temperature Thickness Gas pair Permeanceb [10− 8
mol m− 2
Selectivity Ref.
materials orientation [oC] [μm] s− 1⋅Pa− 1]

Aperture Size Adjustment CuBTC -a 25 20 H2/CH4 200 6.5 [27]

CuBTC/MIL-100 – 17 8.8 335.7
ZIF-67 – 25 3.7 H2/C3H8 40 6.4 [32]
Zn90-ZIF-7 – -c 20 1200
Zn-ZIF-8 – 25 1.1 C3H6/ 2.2 65 [34]
CoZn-ZIF-8 – 1.2 C3H8 2.0 120
1 – 25 36 H2/CH4 182 5.2 [35]
JUC-150 – 33 18.3 26.1
ZIF-8 – 25 3 H2/CH4 52 3.5 [38]
Ambz/ZIF-8 – – 5.1 90.1
GO/ZIF-8 – 250 28 13 139.1 [46]
RHT/ZIF-8 – 25 0.55 27 177 [48]
ZIF-7 – 25 – H2/CH4 15.2 7.5 [41]
ZIF-7-8 – 1.5 8.3 11.6
ZIF-722-8 – 0.45 2.7 71 [42]
Defect Elimination ZIF-8 – 25 6.8 C3H6/ 0.22 94 [60]
C3H8
ZIF-302 – 35 7 H2/CH4 2.8 51.5 [61]
ZIF-8 – 25 3.4 H2/CH4 15 39.1 [63]
ZIF-8 – 25 7 H2/CO2 67 12.3 [64]
UiO-66 – 25 1.6 CO2/N2 4 31.3 [65]
ZIF-8/rGO – 170 0.014 H2/CO2 957 26.4 [67]
MXene – 25 0.8 H2/CO2 12.7 44 [68]
MXene-ZIF-8 – 25 0.8 5.97 77
COF-300/UiO-66 – 25 120 H2/CO2 30.2 32.9 [70]
ZIF-90 – 200 20 H2/CO2 25 7.3 [73]
ZIF-90/MEA – 200 20 1.4 62.5
ZIF-8 – 25 0.1 C3H6/ 1.28 30 [76]
ZIF-8/Mn(acac)2 – 25 0.1 C3H8 0.6 210
ZIF-8 – 25 2.2 C3H6/ 2.85 40 [78]
ZIF-8/PDMS – 25 2.2 C3H8 2.25 95
Thinning Membranes ZIF-7-8 – 25 0.5 CO2/CH4 – 25 [82]
Thickness ZIF-8 – 25 0.5 C3H6/ 6.09 142 [84]
C3H8
ZIF-8 – 25 0.5 C3H6/ 9.9 31.6 [85]
C3H8
Zr-fum-fcu-MOF – 25 0.15 C3H6/ 3.6 127 [86]
C3H8
Co2(bIm)4 – 30 0.06 H2/CO2 17.2 58.7 [87]
Zn2(bIm)4 – 30 0.2 H2/CO2 14 106 [88]
Zn2(bIm)4 – 120 0.001 H2/CO2 90.45 291 [89]
Zn2(bIm)3 – 120 0.01 H2/CO2 80 166 [90]
2D MAMS-1 – 25 0.04 H2/CO2 24 245 [91]
ZIF-L – 25 0.03 CO2/CH4 154 21 [92]
ZIF-8 – 25 0.62 C3H6/ 27 150 [96]
C3H8
ZIF-8 – 25 0.55 H2/CO2 63.1 43 [97]
Ni3(HITP)2 – 25 0.6 CO2/N2 159 10.2 [98]
DZIF-8 – 25 0.04 C3H6/ 67 90 [99]
C3H8
ZIF-67 – 25 0.28 CO2/N2 201 34 [100]
ZIF-L – 25 0.15 H2/CO2 134 200 [101]
ZIF-8 – – 0.02 C3H6/ 28 70 [102]
C3H8
Orientation Adjustment Cu3(BTC)2 010 25 20 H2/N2 0.22 23 [105]
Cu3(BTC)2 – – 214 7.04
ZIF-8 100 25 12 H2/CH4 10 18 [104]
ZIF-8 110 1.1 11.8 14 [113]
ZIF-8 – 1 17 13
ZIF-95 C 25 1.5 H2/CO2 19 184 [110]
ZIF-95 C 100 0.02 79 32.2 [111]
ZIF-95 – 20 8.6 25.5
ZIF-67 002 25 50 H2/C3H8 60 48 [118]
ZIF-67 – – 40 6.4 [32]
ZIF-L B 25 5 H2/CO2 17 5.5 [108]
ZIF-L C 5 19.5 24.3

Note:
a
Random orientation.
b
Permeance of the smaller gas molecules in the two components.
c
Membranes thickness is unknown.

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H. Lian et al. Results in Engineering 15 (2022) 100609

partially substituting Fe3+ for Cu2+ in the CuBTC structure (Fig. 3a) and
competitive molecular sieving capabilities were also achieved [27]. The
H2/CH4 selectivity of the CuBTC/MIL-100 membrane increased to
335.7, which was 26 times higher than that of the control CuBTC
membrane; H2 permeance retained at 1 × 10− 7 mol m− 2 s− 1⋅Pa− 1
(~4200 Barrer) (Fig. 3b).
Our group successfully prepared a continuous Zn–Co-ZIF-67 poly­
crystalline membrane with excellent C3H6/C3H8 separation perfor­
mance through fine-tuning of the effective pore aperture by Zn2+
substitution in the ZIF-67 framework [32]. The partially replaced Co2+
(larger ionic radius) by Zn2+ ion (shorter ionic radius) in the ZIF-67
framework generated shorter Zn–N bonds (than Co–N), contributing to
the narrowed aperture size and, therefore, the improved separation
factor. The separation factor for C3H6/C3H8 increased from 1.4 to 50.5 at
90% Zn2+ loading and C3H6 permeance retained 1 × 10− 8 mol m− 2
s− 1⋅Pa− 1, which the separation performance is comparable to that of
ZIF-8 membrane. Following this work, Wang et al. [33] synthesized a
series of Zn/Co-ZIF membranes by introducing Zn2+ into the precursor
solution of ZIF-67 membranes using the fast current driven-method. The
Zn/Co-ZIF membranes have a smaller aperture and better grain
boundary structure compared with ZIF-67, which is beneficial to
improving membrane separation performance. The C3H6/C3H8 separa­
tion factor is further improved to 200 and C3H6 permeance reached 2 ×
10− 8 mol m− 2 s− 1⋅Pa− 1. Jeong et al. [34] also synthesized Co–Zn-ZIF-8
membranes by the rapid microwave-assisted method. The C3H6/C3H8
separation factor increased from 63 to 120 compared with the ZIF-8
membrane and C3H6 permeance reached 2 × 10− 8 mol m− 2 s− 1⋅Pa− 1
due to the increased stiffness of metal-nitrogen bounds and reduced
effective aperture size in ZIF-8 membrane by Co2+ ion addition.
2.1.2. Ligand doping
The aperture size can also be precisely adjusted by introducing a new
ligand or partially replacing the original ligand in the MOF framework.
The newly introduced ligands can also enhance the interaction between
the gas molecule and the framework, thus further improve the separa­
tion performance. For example, introducing higher polar ligands with a
stronger affinity of CO2 will benefit the interaction between the CO2 gas
molecule and the ligand dopped MOF, therefore, the enhanced CO2
adsorption capacity. Qiu et al. [35] prepared JUC-150 membranes with
smaller aperture sizes by replacing the original 4,4′ -bipyridine with a
shorter pillar ligand pyrazine. Later, the same group fabricated a
JUC-160 membrane with mixed-ligand that has a unique ZIF structure
constructed by two bulk imidazolate linkers (2-methylbenzimidazole
and benzimidazole) [36]. The methyl group and bulk phenyl rings on
imidazolate linkers fill in the void space inside the JUC-160 framework,
resulting in a reduced aperture size that can block CO2 molecules and
realize the separation of the gas pair of H2/CO2. The H2/CO2 separation
factor was up to 26.3 and H2 permeance reached 9.75 × 10− 7 mol m− 2
s− 1⋅Pa− 1 at 200 oC. Recently, Zhao et al. [37] prepared continuous a
MIL-160/CAU-10-F membrane by adding the ligand 5-fluoroisophthalic
acid into the MIL-160 framework by in situ hydrothermal synthesis. The
introduced larger size of 5-fluoroisophthalic acid ligand than 2,

Fig. 3. (a) Schematic illustration of CuBTC/MIL-100 pore structures. (b) Comparison of CuBTC/MIL-100 membranes with other membranes for H2/CH4 system. (c)
Comparison of effective pore aperture of ZIF-8, ZIF-7 and mixed linker ZIF-7-8. (d) CO2/CH4 separation performance of ZIF-7-8 membranes. (e) Adsorption isotherms
and (g) the IAST adsorption selectivity of ZIF-8 for C3H6/C3H8. (f) Schematic representation of the DMAc@ZIF-8 for C3H6/C3H8 separation. Reproduced with
permission from Refs. [27,41,43]. Copyright 2016 Nature Publishing Group. Copyright 2018 American Chemical Society. Copyright 2020 Wiley-VCH.

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H. Lian et al.
5-furandicarboxylic acid ligand used in MIL-160 resulted in an overall
reduced aperture size in MIL-160/CAU-10-F membrane that limits
diffusion rate of CH4 leading to the increased CO2/CH4 selectivity by
10.7%. Meanwhile, the higher polarity of 5-fluoroisophthalic acid
ligand also showed a higher adsorption capacity of CO2 than 2,5-furan­
dicarboxylic acid ligand used in MIL-160, therefore, a simultaneous
improved CO2 permeance (31.2% up) was recorded.
Tsapatsis et al. [38] prepared ZIF-8 membranes by incorporating
2-aminobenzimidazole into the framework using a vapor phase ligand
treatment. The smaller pore size of the membrane resulted in a notable
shift of the molecular level cut-off to smaller molecules. The H2/N2
selectivity increased from 5.2 to 126 and H2 permeance reached ~1.5 ×
10− 7 mol m− 2 s− 1⋅Pa− 1. The performance is superior to other MOF
membranes reported, which are expected to be used in industrial ap­
plications in the future. Our group then fabricated a high-quality ZIF-8
membrane by doping 2-aminobenzimidazole into the ZIF-8 framework
for effective separation of the C3H6/C3H8 mixture [39]. The effective
aperture of the ZIF-8 framework was slightly reduced due to the incor­
poration of the larger-sized ligand. The C3H6/C3H8 separation factor
increased to 67 and C3H6 permeance reached 1.34 × 10− 8 mol m− 2
s− 1⋅Pa− 1. More importantly, the membrane separation performance is
significantly improved under high pressure and high temperature con­
ditions, which is conducive to future industrial applications. Similarly,
Jeong et al. [40] synthesized a ZIF-8 membrane with high gas per­
meance by partially exchanging 2-methylimidazole with the 2-imidazo­
lecarboxaldehyde ligand. The C3H6 permeance of exchanged ZIF-8
membrane is about 4 times higher than that of the original membrane
while retaining the C3H6/C3H8 separation factor. Furthermore, they also
obtained ZIF-7-8 membranes with mixed linkers by hybridizing 2-meth­
ylimidazolate (ZIF-8 linker) and benzimidazolate (ZIF-7 linker) through
a rapid one-pot microwave method [41]. The incorporation of larger
benzimidazolate ligands reduces the effective aperture size of ZIF-8 from
4.0 Å to ~3.0 Å (Fig. 3c), which leads to enhanced CO2/CH4 selectivity
(Fig. 3d). Wang et al. [42] also synthesized ZIF-722-8 membranes by a
fast current-driven method. The ZIF-722-8 membrane exhibited a tenfold
higher separation factor for CO2/CH4 mixtures of up to 25 which is
significantly higher than other ZIF-8 membranes.
2.1.3. Framework flexibility control
The MOF framework with high flexibility would lose its molecular
sieving ability due to the additional diffusion of larger kinetic diameters
of gas molecules. This is caused by the rotation or in-situ vibrations of
ligands that results in lattice motion and changeable aperture size.
Therefore, flexibility control and adjustment of the effective aperture in
MOF structure are two key factors to achieve the targeted specific
membrane separation performance [44]. Preferable MOF membrane
with a more rigid lattice structure generally has high separation effi­
ciency. For example, the rigid ZIF-8 membrane prepared in Wang’s
group exhibited a C3H6/C3H8 separation factor higher than 300 [45].
This sharp molecular sieving property is attributed to the
inborn-distorted and stiff MOF framework resulting from the assembly
of metal ions and ligands through a fast current-driven method. Simi­
larly, the flexibility inhibited ZIF-8@GO membrane also showed a high
H2/CH4 selectivity which was up to 139 in Huang’s study [46]. This is
achieved through the layer-by-layer deposition method in which the
rigid GO layer can fill the gaps between ZIF-8 crystals by capillary force
and covalent bond force. The flexibility of two-dimensional MOF ul­
trathin nanosheets (MONs, Cu(dhbc)2(bpy)⋅H2O) membranes can be
further confined between graphene oxide nanosheets (GONs) and lead to
a CO2-induced gate opening and closing behavior which is responsible
for the sharp increase of CO2 permeance (from 5.82 × 10− 8 to 3.83 ×
10− 7 mol m− 2 s− 1⋅Pa− 1) and CO2/CH4 selectivity (from 4.1 to 22.8)
[47]. Post-heat treatment can also generate a relatively rigid MOF
membrane with retained crystallinity. For example, a more rigid ZIF-8
membrane was obtained under a rapid heat treatment for 15 s and the
H2 permeance and H2/CH4 selectivity reached 2.7 × 10− 7 mol m− 2
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Results in Engineering 15 (2022) 100609
s− 1⋅Pa− 1 and 175, respectively [48]. Furthermore, thermal or chemical
activation could affect the flexibility of MOF structure as well [49]. The
flexibility in MOF refers to the lattice motion and aperture size change
resulting from rotation or in-situ vibrations of ligands caused by thermal
or chemical treatment. For example, the pore diameter was ~3.7 Å in
flexible MOF (Zn-AIPAZPY) when it was thermally activated whereas,
the pore size changed to 2.92 Å when chemically activated by methanol
washing.
2.2. Cage functional modification
Porous MOF material exhibits different affinity, adsorption, and
permeation performances towards individual gas molecules due to their
diverse microstructures and functionalities. The gas separation perfor­
mance of MOF membrane, especially for selectivity, can be enhanced by
precise cage structure modification including mainly in situ synthesis
[50] and post-synthesis treatment [51].
2.2.1. In situ synthesis
Adsorption properties and diffusion rates of gases in a MOF cage
determine the separation performance of MOF membranes. A close
interaction between the cage and gas molecules is usually associated
with improved separation performance in MOF membranes [52]. For
example, a dense NH2-MIL-53 membrane prepared by a secondary
growth method with strong adsorption ability for a larger molecule of
CH4 gas can suppress its diffusion rate and result in a high selectivity of
20.7 for H2/CH4 and permeance of 1.5 × 10− 7 mol m− 2 s− 1⋅Pa− 1 for H2
[53]. Similarly, dense sod-ZMOF-1 membranes constructed from the
assembly of In (III) cations and imidazoledicarboxylate linkers in the
presence of structure directing agents (SDAs) were prepared by a sol­
vothermal crystallization method in the Eddaoudi group [54]. The
unique anionic characteristic of the membrane is prone to interact with
the quadruple CO2. The smaller aperture window size (4.1 Å) also makes
it suitable for CO2 separation. Consequently, the membrane selectivity
for CO2/H2 (5.2) was higher than the ideal selectivity. Besides, guest
molecules can also be confined in a MOF cage to regulate the molecular
sieve fraction performance [55]. The homogeneous guest molecules
distribution in the channel not only can reduce the window size but also
enhance the interaction between MOF and CO2. Therefore, the mem­
brane of narrowed window size with restricted CO2 diffusion rate
property can be formed and contribute to a higher H2/CO2 selectivity.
Recently, Li et al. [43] synthesized high-quality ZIF-8 membranes using
water and dimethylacetamide as solvents through rapid semi-solid
processing. The residual dimethylacetamide in the cage showed higher
adsorption selectivity for C3H6/C3H8 (up to 190) than that of other ZIF-8
membranes (Fig. 3e–g).
2.2.2. Post-synthesis processing
The solvent and the uncoordinated excess ligands are usually trapped
in the cage after the synthesis of the MOF membrane. These residuals
would greatly affect the affinity towards gases and gas transportation
behavior in the MOF membrane. Activation is the key step to opening
the cage structure for gas transportation through the MOF membrane.
For example, the solvent of water in the ZIF-8 cage can be removed by
solvent-exchange and slow evaporation operation leading to an
improved C3H6/C3H8 separation factor from 30 to 90 [56]. The online
activation is another way to remove DMF solvents from the ZIF-7-NH2
membrane resulting in a cracks-free ZIF-7-NH2 membrane with an
increased separation factor of H2/CO2 in the binary mixture from 1 to 19
[57]. The online activation here refers to monitoring the activation
process by streaming activation experiments using binary mixtures.
2.3. Defect elimination
The defect in polycrystalline MOF membranes is another major issue
that seriously affects their gas selectivity. Various methods have been
H. Lian et al.
developed to fabricate defect-free continuous MOF membranes for
efficient gas separation. To give readers an overall understanding, the
recent progress towards this is summarized in this section. These mainly
include in situ synthesis (such as adding modulator, developing novel
methods and synthetic bilayer membranes) and post synthetic modifi­
cation (such as chemical modification and physical polymer coating).
2.3.1. In situ synthesis modification
One of the challenges in the preparation of MOF membranes is to
promote the heterogeneous nucleation of MOFs on the substrate surface
and inhibit the homogeneous nucleation in the solution bulk phase.
Therefore, fast or slow nucleation and growth rates of MOF crystals can
seriously affect the crystal growth and membrane density on the surface
of the support. The defect-free MOF membranes were prepared by
adding a modulator to control nucleation/growth rate in a traditional
approach [58]. For example, polydopamine was initially found in a
study that can improve MOF membrane density by adding Zn(II)-doped
polydopamine (Zn-PDA) in the ZIF-8 membrane synthesis process [59].
Subsequently, a more detailed investigation to reveal the function of
modulator addition on defect-free MOF membrane formation was con­
ducted in Shao group [60]. Dopamine, as a modulator in a ZIF-8 syn­
thetic solution, largely inhibited the homogenous nucleation of ZIF-8
crystals during in situ polymerization process and the resultant
counter-diffusion growth mechanism of ZIF-8 was responsible for the
repair of possible defects (Fig. 4a). Therefore, a high C3H6/C3H8 sepa­
ration factor (up to 94) and C3H6 permeability was achieved (45 Barrer,
Fig. 4d). In addition, sodium formate was used as a modulator in our
recent study, a continuous ZIF-302 membrane with excellent gas sepa­
ration performance was prepared for the first time [61]. The weakly
alkaline modulator effectively controlled the nucleation and growth rate
of ZIF-302 crystal, resulting in a seed layer with uniform particle size
distribution which would provide a good base for the subsequent growth
of ZIF-302 membrane. The resultant membrane showed a H2/CH4
selectivity of 51.5 and H2 permeance of 2.8 × 10− 8 mol m− 2 s− 1⋅Pa− 1.
The membrane performance for H2/CH4 obviously exceeds the Robeson
upper bound in 2008, indicating that the membrane materials possess
Fig. 4. Schematic illustration of (a) ZIF-8/PDA hybrid membranes in the presence of dopamine (b) ZIF-8/rGO membrane by in situ crystallization and (c) ZIF-8
membrane coated with a layer of PDMS. (d) The separation performance of the ZIF-8/PDA membrane for C3H6/C3H8 mixtures. (e) Comparison of the H2/CO2
separation performance of the prepared MOF/GO membranes. (f) Scatterplot of improved C3H6/C3H8 selectivity on ZIF-8 membranes. Reproduced with permission
from Refs. [60,67,78]. Copyright 2019 Royal Society of Chemistry. Copyright 2016 Royal Society of Chemistry. Copyright 2017 Royal Society of Chemistry.
6
Results in Engineering 15 (2022) 100609
potential application value for the H2/CH4 separation.
Some novel preparation methods towards defect elimination were
also explored. Jeong’ group [62] employed rapid thermal deposition
techniques to fabricate continuous well-grown HKUST-1 and ZIF-8
membranes in a relatively short period of time. The rapid solvent
evaporation rate drove the precursor solution to diffuse from inside to
the outside of the supports resulting in crystallization occurrence on
both sides of the supports. As a result, the grain boundary structure was
smoothed/optimized, and gas separation performance was significantly
improved. On the other hand, the solvent-free method is another option
to prepare continuous MOF membranes (ZIF-8, ZIF-69, ZIF-9) [63]. This
was achieved by converting the highly active metal precursor layer into
MOF membranes without the assistance of solvents. This avoids the
adverse effect of solvent on the grain boundary structure and usually
leads to a desirable MOF membrane separation performance. For
instance, ZIF-8 membrane synthesized by this method has H2/CH4
selectivity of 39.1 and H2 permeance of ~1.5 × 10− 7 mol m− 2 s− 1⋅Pa− 1.
Same technique was applied in Qiu et al.‘s work [64] which also shows
high separation performance with H2 permeance of 6.7 × 10− 7 mol m− 2
s− 1⋅Pa− 1 and H2/CO2 selectivity of 12.3. Furthermore, tertiary sol­
vothermal growth methodology is adopted in Liu et al.‘s work and shows
similar effect [65]. The homogenous UiO-66 crystal nucleation and
growth in the bulk solution were suppressed by using layered ZrS2 as
zirconium source, and grain boundary defects were reduced by tertiary
solvothermal growth. A continuous UiO-66 membrane with high
CO2/N2 separation performance was obtained. The selectivity of UiO-66
membrane for CO2/N2 was up to 31.3 and CO2 permeance reached 4 ×
10− 8 mol m− 2 s− 1⋅Pa− 1.
A bilayer composite membrane structure can also help to prevent the
defects occurring in polycrystalline MOF membrane. A series of MOF-
based composite membranes have shown impressive separation per­
formances [66]. For example, the in situ crystallized ZIF-8 nanosheets
between the layers of reduced graphene oxide (ZIF-8/rGO) showed high
quality of composite membrane due to the strong anchor and bolster up
rGO by coordination bonds (Fig. 4b) [67]. This was accompanied by a
high membrane separation performance with H2/CO2 selectivity
H. Lian et al.
reaching about 26.4 and H2 permeability reaching ~400 Barrer
(Fig. 4e). Moreover, Wang et al. [68] successfully synthesized a free­
standing MXene-ZIF-8 dual-layered membrane for hydrogen separation
by combining electrophoretic deposition and fast current-driven syn­
thesis. The prepared composite membrane has no obvious defects and
cracks, and the H2/CO2 selectivity increases from 44 to 77 with H2
permeance of 5.97 × 10− 8 mol m− 2 s− 1⋅Pa− 1. Furthermore, Ben et al.
[69] prepared COF/MOF composite membranes to achieve
defects-reduced and higher H2/CO2 mixture separation selectivity. They
later prepared COF-300/UiO-66 composite membranes with unprece­
dented H2/CO2 gas mixture selectivity (32.9) as well as ultrahigh H2
permeability (108341.3 Barrer) [70]. This was due to the synergy
function between COF and MOF where a strong chemical bond formed
in a specially designed MOF membrane. This exclusive membrane ar­
chitecture endows the membrane with superb permeability arising from
the columnar π-arrays of 2D COFs that provide direct pathways for gas
flux and exceptional selectivity resulting from the formation of an in­
termediate layer between the 2D COF and 3D MOF matrices that seal the
space between the grain boundaries and enhance the gas selectivity
[70].
2.3.2. Post synthetic modification
Post modification method provides more options to eliminate the
defects/non-selective transport pathways in MOF membranes and
improve the gas selectivity. The chemical modification of MOF mem­
brane is helpful to minimize non-selective transport through intercrys­
talline gaps [71], or physical modification of MOF membrane is also
obtained by repairing the defects in the membrane [72]. The
as-synthesized ZIF-90 membrane was chemically post-functionalized by
ethanolamine condensation leading to the H2/CO2 selectivity increased
from 7.3 to 62.5, and H2 permeance decreased to 1.4 × 10− 8 mol m− 2
s− 1⋅Pa− 1 [73]. The as-synthesized ZIF-90 membrane was also immersed
into a solution of 3-aminopropyltriethoxysilane (APTES) in methanol for
amine condensation. The inter-crystalline defects were reduced by the
chemical post-functionalization and the relatively large APTES was
restrained from entering the ZIF-90 interior [74]. Therefore, the mem­
brane with high H2 permeance of about 2.9 × 10− 7 mol m− 2 s− 1⋅Pa− 1
and H2/CH4 selectivity of 71 was obtained. Similarly, the separation
performance of Mg-MOF-74 membrane was also improved by the
post-modification with ethylenediamine, which was attributed to the
strong CO2 adsorption ability from amine groups [75]. Moreover, Tsa­
patsis’s team significantly improved the separation performance of the
ZIF-8 membrane by the vapor-phase manganese (II) acetylacetonate
treatment [76]. The C3H6/C3H8 selectivity increased from 31 to 210 and
C3H6 permeance reached ~6 × 10− 9 mol m− 2 s− 1⋅Pa− 1.
Polymer coating can effectively seal the defects in MOF structure and
improve the gas separation performance of MOF membrane [77]. Our
group coated polydimethylsiloxane (PDMS) on the surface of the syn­
thesized ZIF-8 membrane [78]. The PDMS coating solution penetrated
into the underneath of ZIF-8 membrane and blocked the inter-crystalline
defects, thus enhanced C3H6/C3H8 separation performance (Fig. 4c).
The C3H6/C3H8 selectivity of PDMS/ZIF-8 membrane increased from 40
to 95 (Fig. 4f). Consistently, our group further applied this strategy to
improve separation performance of tubular ZIF-8 membranes for
C3H6/C3H8 [79]. Tubular ceramic supports were selected due to their
high mechanical strength and large packing density. The C3H6/C3H8
separation factor increased from 12 to 67 and H2 permeance reached
1.3 × 10− 8 mol m− 2 s− 1⋅Pa− 1. The strategy can repair intergranular
defects without affecting gas permeance, making ZIF-8 membrane a
potential commercial application.
3. Manipulation strategies for permeance
Gas permeance has the key responsibility for the product recovery
rate and membrane cost. This section highlights several main factors
that significantly affect MOF membrane permeance performance
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Results in Engineering 15 (2022) 100609
including the membranes thickness control and orientation adjustment.
The separation performance of MOF membrane corresponding to typical
manipulation strategies for permeance is summarized in Table 1.
3.1. Membranes thickness control
The gas permeance of MOF membranes can be significantly
improved by reducing membrane thickness [80]. However, the MOF
membranes prepared by traditional methods usually exhibit larger
membrane thickness. For example, the MOF-5 membrane fabricated by
the secondary growth method was 40 μm for gas separation application
[81]. To meet the high gas permeance requirements of MOF membranes,
novel synthesis methods have been developed to prepare thinner MOF
membranes (less than 1 μm). These mainly include electrochemical
deposition, 2D MOF nanosheets deposition, interfacial synthesis and
sol-gel method.
3.1.1. Electrochemical deposition
The electrochemical deposition has emerged as a novel approach to
fabricate MOF membranes. This approach requires shorter synthesis
time and milder synthesis condition compared with conventional sol­
vothermal synthesis. The formation of the insulating MOF layers will
hinder the further contact between the mother solution and the elec­
trode surface, and thus the current-driven membrane growth will stop
automatically with increasing time. Therefore, the approach can be
employed to prepare ultra-thin MOF membranes. For example, Wang
et al. fabricated a hybrid ZIF-7-8 membrane by fast current-driven
synthesis with a membrane thickness of only 500 nm [82]. ZIF-8
membranes with a thickness of 840 nm were also successfully pre­
pared within 1 h via the same strategy [83]. These ZIF-8 membranes
showed excellent separation performance with H2 permeance of ~3.5 ×
10− 7 mol m− 2 s− 1⋅Pa− 1. Later, Lai et al. developed an aqueously
cathodic deposition approach to fabricate ZIF-8 membrane without any
supporting electrolyte or modulator [84]. The preparation process uti­
lizes water as the only solvent and a thickness of 500 nm ZIF-8 mem­
brane was obtained without any pre-synthesis treatment. The membrane
exhibited superior performance in C3H6/C3H8 separation compared
with traditional solvothermal synthesis of the membrane, and the C3H6
permeance and C3H6/C3H8 selectivity were 6.09 × 10− 8 mol m− 2
s− 1⋅Pa− 1 and 142, respectively. To further improve C3H6 permeance,
Agrawal et al. [85] prepared a defect-free ZIF-8 membrane with a
thickness of 500 nm through a novel electrophoretic nuclei assembly
strategy (Fig. 5a). The method utilized electrophoretic deposition of
ZIF-8 nuclei from the precursor sol onto a substrate under an external
direct current electric field. ZIF-8 nuclei were further grown in the same
precursor sol, resulting in a highly intergrown ZIF-8 membrane. It has an
ultra-high C3H6 permeance of 9.9 × 10− 8 mol m− 2 s− 1⋅Pa− 1 which is
obviously better than the performance reported in the literature.
Furthermore, Eddaoudi et al. prepared nine isoreticular fcu-MOF
membranes with various metal clusters and organic linkers through
electrochemical directional assembly strategy [86]. The membrane
thickness was controlled within the range of 75 nm and 891 nm. The
triangular pore apertures of Zr-fum-fcu-MOF, constrained by fumarates
with non-rotating C– – C double bonds, provides higher separation per­
formance. The C3H6 permeance of Zr-fum-fcu-MOF membrane reached
3.6 × 10− 8 mol m− 2 s− 1⋅Pa− 1 (108 GPU, 1 GPU = 3.35 × 10− 10 mol m− 2
s− 1⋅Pa− 1) which was 1–3 times higher than other reported membrane
performance [16].
3.1.2. Nanosheets deposition
Two dimensional (2D) MOFs nanosheets are known as an ideal op­
tion for MOF membrane fabrication with ultra-thin thickness and
extremely low mass-transfer barrier, which can greatly improve the gas
separation permeance. For example, Nian et al. prepared the 2D
Co2(bim)4 nanosheet membrane with the thickness of 57 nm via ligand
vapor phase transformation of the Co-based gel layer [87]. The gel layer
H. Lian et al.
Fig. 5. (a) Schematic illustration of the ENACT process for the synthesis of MOF films. (b) Cross-sectional view of Zn2(bim)4 nanosheet layer on α-Al2O3 support and
(c) H2/CO2 the average selectivity of the membranes prepared at different coating temperatures. (d) Schematic illustration of membrane synthesis using the counter-
diffusion method. (e) Zn gel layer on PVDF hollow fiber is transformed into ZIF-8 membranes under ligand vapor environment. Reproduced with permission from
Refs. [85,89,95,102]. Copyright 2018 Wiley-VCH. Copyright 2014 American Association for the Advancement of Science. Copyright 2013 American Chemistry
Society. Copyright 2017, Nature Publishing Group.
can provide active metal sources, guiding the oriented growth of the
nanosheets and controlling the membrane thickness. The 2D ultra-thin
membrane shows excellent performance for H2/CO2 with ideal selec­
tivity of 58.7 and the H2 permeance of 1.72 × 10− 7 mol m− 2 s− 1⋅Pa− 1.
Based on this, Zhang et al. prepared a Zn2(bim)4 membrane by
employing graphene oxide to guide the self-transformation of ZnO
nanoparticles and controlled the thickness by changing the thickness of
ZnO layer [88]. The membrane thickness was about 200 nm. Thus, the
membrane showed excellent H2/CO2 separation performance with the
H2 performance of 1.4 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and the ideal separation
selectivity of about 106.
Surprisingly, Yang et al. successfully constructed a ~1-nm-thick 2D
membrane by depositing a few Zn2(bim)4 disordered nanosheet layers
on the support surface (Fig. 5b) [89]. These isolated Zn2(bim)4 nano­
sheets can be obtained by exfoliating layered Zn2(bim)4 bulk through a
wet ball-milling and volatile solvent ultrasonication techniques. The
resultant membrane had a high H2 permeance of 9 × 10− 7 mol m− 2
s− 1⋅Pa− 1 (2700 GPU) and a high H2/CO2 selectivity of 291 (Fig. 5c).
They also prepared 10-nm-thick ultra-thin Zn2(bim)3 membrane by the
hot-drop coating technique [90]. The formed membrane demonstrates
an excellent H2/CO2 separation performance, with a H2 permeance of up
to 8 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and separation factor of up to 166, which
is very attractive for industrial applications. Wang et al. also prepared
the 40-nm-thick MAMS-1 membrane by hot-drop casting method [91].
These isolated nanosheets can be obtained by exfoliating layered
MAMS-1 crystals through a freeze-thaw approach in suitable solvent
systems. The H2/CO2 separation selectivity and H2 permeance were 245
and 2.4 × 10− 7 mol m− 2 s− 1⋅Pa− 1 respectively. Recently, Zhong et al.
successfully prepared ultra-thin ZIF-L membranes with the thickness of
27.8 nm via in-situ interface exfoliation for CO2/CH4 separation [92].
The growth of ultra-thin nanosheets is attributed to inadequate
competitive adsorption between the free and riveted crystal nuclei on
the sub-nano region near the interface. The CO2 permeance of ultra-thin
ZIF-L membrane was up to 1.54 × 10− 6 mol m− 2 s− 1⋅Pa− 1 (4600 GPU),
and the CO2/CH4 selectivity reaches 21. This is the best separation
performance reported so far and is expected to be used in industrial
applications.
8
Results in Engineering 15 (2022) 100609
3.1.3. Interfacial synthesis method
The ultrathin MOF membranes can also be fabricated by confining
the nucleation and growth of MOFs to the solution interfaces. MOF
crystals immediately begin to nucleate and crystallize on the substrate
when the metal and ligand solutions come into contact, and eventually
grow into a dense membrane [93–98]. Jeong et al. prepared high-quality
ZIF-8 membrane by contra-diffusion method [95]. This mainly depends
on the contact, collision, nucleation and crystallization of the reactants
at the interface (Fig. 5d). The ZIF-8 crystals can only grow at the
interface between the support surface and precursor solution, so the
interface limits the further growth of the crystal, and thus the thickness
of the membrane was controlled under 1.5 μm. The C3H6 permeance
reached ~2 × 10− 8 mol m− 2 s− 1⋅Pa− 1 and the C3H6/C3H8 selectivity
reached ~55. Moreover, Peinemann et al. prepared 620-nm-thick ZIF-8
membrane on the polythiosemicarbazide support by the same method
[96]. The H2 permeance and C3H6/C3H8 selectivity were 2.7 × 10− 7 mol
m− 2 s− 1⋅Pa− 1 and 150, respectively. To further improve gas permeance,
the continuous and ultra-thin ZIF-8 membrane was prepared by
contra-diffusion method in a confined space [97]. The nucleation and
growth of ZIF-8 crystals were controlled by employing a
polydopamine-wrapped single-walled carbon nanotube network as an
interlaminar medium for different liquids. This resulted a membrane
with thickness of 550 nm and H2 permeance improved to 6.31 × 10− 7
mol m− 2 s− 1⋅Pa− 1. Recently, the continuity Ni3(HITP)2 membrane with
thickness of 600 nm was also prepared based on the same
contra-diffusion method [98]. The CO2 permeance and CO2/N2 selec­
tivity were 1.59 × 10− 6 mol m− 2 s− 1⋅Pa− 1 and 10.2, respectively. The
separation performance exceeds that of most MOF membrane materials
and has the potential for further development.
Interface layer polarization induction strategy was adopted to pre­
pare ultrathin low-crystallinity MOF membranes [99]. These were
achieved using the interface layer with dense and uniform distribution
of metal ions, resulting in the creation of abundant open metal sites, and
thus enhanced the facilitated transport properties of olefin molecules.
Among these membranes, the ZIF-8 membranes modified in situ with
diethanolamine showed smaller thickness (73 nm) and the unprece­
dented C3H6/C3H8 separation performance with C3H6 permeance
H. Lian et al.
(6.7–10.6 × 10− 7 mol m− 2 s− 1⋅Pa− 1) and C3H6/C3H8 selectivity
(90–120). The membrane performance had met the requirements of
industrial applications. Similarly, the continuous ultra-thin ZIF-67
membranes was also prepared at PVA-Co2+ interface by the same
methods [100]. PVA-Co2+ interface not only increased the rate of het­
erogeneous nucleation at the interface, but also promoted the in-situ
repair of crystal nucleus layer. The CO2 permeance and CO2/N2 selec­
tivity of 280-nm-thick ZIF-67 membranes reached 2.01 × 10− 6 mol m− 2
s− 1⋅Pa− 1 (6000 GPU) and 34, respectively. The separation performance
become one of the most promising membranes for industrial application.
Yang et al. imbedded ZIF-L membranes completely into the voids of the
support by the interfacial assembly method, showing
apparent-zero-thickness apart from the support surface [101]. These
membranes formed in the confined space provided a complete mem­
brane interlocked support (MIS) composite structure. The H2 permeance
and H2/CO2 separation factor exceeded 1.3 × 10− 6 mol m− 2 s− 1⋅Pa− 1
(4000 GPU) and 200, respectively. This performance represented that
ZIF-L membranes create a new high separation performance record and
become one of the most promising membranes for industrial application.
However, the scale-up preparation of the large membrane area and
long-term stability are the main factors limiting its industrial
application.
3.1.4. Sol-gel method
The sol-gel method can also be used to prepare high-performance
ultra-thin MOF membranes. It is characterized by good uniformity of
membrane formation and strong adhesion to the support. This method
can make membrane with a controllable thickness and gas permeance of
several orders of magnitude higher than that of membrane fabricated
through the conventional method. For example, homogeneous ZIF-8
membranes prepared from sol-gel coating and vapor deposition
method had thickness of 17 nm with H2 permeance and C3H6/C3H8
selectivity of 2.15 × 10− 5 mol m− 2 s− 1⋅Pa− 1 and 70, respectively
(Fig. 5e) [102]. ZIF-8 membranes with controllable thickness (130 nm)
were also prepared by a similar method transformation [103]. The high
nucleation density of gel coating improved the symbiosis of poly­
crystalline layer leading to membrane with strong grain boundary
structure and excellent gas separation performance. The H2 permeance
was improved to 3.15 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and C3H6/C3H8 selec­
tivity was 200. Compared with the traditional MOF membranes pre­
pared by crystallization in precursor solution, this method can greatly
reduce the consumption of solvent and precursor.
3.2. Orientation adjustment
The continuous dense MOF membranes are effective for gas sepa­
ration but suffer from low gas permeance. Oriented MOF membranes
have been proven to benefit gas permeance due to the aligned pore
channels which can significantly reduce diffusion resistance. Moreover,
more exposure chance for the effective pore sizes and reduction of grain
boundary defects also contribute to the enhanced gas separation per­
formance. Various methods have been summarized in this study to
prepare the oriented MOF membranes. These mainly include in situ
modification, MOF seeds-oriented deposition and metal oxide nanorods-
oriented deposition.
3.2.1. In situ modification
The nucleation and crystallization of MOF occur simultaneously in
the bulk solution and the solution-matrix interface. This makes it diffi­
cult to precisely control the orientation of MOF membranes in the in situ
growth method. The oriented MOF membranes can be prepared by
solvothermal reactions on the modified support [104]. Tsapatsis et al.
[105] successfully produced b-oriented microporous MOF (MMOF)
membranes by the seeded growth method. MMOF with 1D channel is
composed of copper paddle-wheel and a V-shaped dicarboxylate ligand.
A randomly oriented seed layer was deposited on the polyethyleneimine
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Results in Engineering 15 (2022) 100609
modified support which would contribute to an oriented growth of
membrane in the secondary growth process due to the competitive grain
growth. The membrane exhibited H2 permeance of ~1 × 10− 8 mol m− 2
s− 1⋅Pa− 1. Recently, the well-intergrown Cu-TCPP with highly c-oriented
ultrathin membranes (ca. 80 nm-thick) were fabricated by in-situ sol­
vothermal method [106]. This was obtained by adding triethylamine to
the precursor solution to control the oriented growth of Cu-TCPP crystal
on an LDH-based ZnO buffer layer-modified support. Regular vertical
stacking of single Cu-TCPP layers along the c-axis through van der Waals
interactions resulted in interlocked interlayer gallery. The membranes
showed H2 permeance of ~3 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and H2/CH4 ideal
selectivity of 56.
3.2.2. MOF seeds-oriented deposition
It is worth noting that the random orientation seed layer deposition
on the support layer leads to the blockage of the 1D straight channel in
the membrane, reducing the gas permeance. Therefore, highly oriented
MOF seed layer is required to prepare oriented MOF membranes with
high gas permeance. Jeong et al. [107] successfully deposited oriented
MOF-5 seeds on the support by microwave-induced thermal deposition
method. With secondary solvothermal growth, the oriented MOF-5
membrane was formed on the orientated seeds layer and showed H2
permeance of ~8 × 10− 7 mol m− 2 s− 1⋅Pa− 1, which was higher than the
non-oriented seed layer membrane. Wang’s group [108] also obtained
b-oriented and c-oriented ZIF-L membrane following the methods of
dip-coating for seed layer as well as and filtration-deposition and a
short-time secondary growth for MOF membrane. The gas separation
results showed that the H2 permeance of b-oriented and c-oriented ZIF-L
membrane reached 4.2 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and 8.4 × 10− 7 mol
m− 2 s− 1⋅Pa− 1, respectively, which is significantly higher than
non-oriented membranes. In addition, Zhu et al. [109] obtained verti­
cally oriented Zn-ZIF-L seed layer by modifying support with polymer.
Then the vertically oriented Co/Zn-ZIF-L membrane was successfully
prepared by heteroepitaxy growth. The Co/Zn-ZIF-L membrane had
significant increased gas separation performance due to the optimized
vertical orientation and grain boundary structure with the CO2 per­
meance reached to 8.2 × 10− 8 mol m− 2 s− 1⋅Pa− 1 (244.9 GPU). More­
over, Huang et al. [110] prepared c-oriented ZIF-95 membrane on the
support coated with c-oriented ZIF-95 seeds layer by solvent-free sec­
ondary growth method. The H2/CO2 separation factors and H2 per­
meance were 184 and 1.9 × 10− 7 mol m− 2 s− 1⋅Pa− 1, respectively, which
were much higher than those of the randomly oriented ZIF-95 mem­
brane. They later prepared highly c-oriented ZIF-95 membrane with
good gas separation performance by vapor-assisted in-plane epitaxial
growth [111]. These were achieved by seeds layer coating on the sup­
port surface by vacuum filtration of a suspension of ZIF-95 nanosheets.
Then the oriented and thin ZIF-95 membrane was formed by in-plane
epitaxial growth in mixed DMF/water vapor atmosphere. The forma­
tion of a highly oriented ZIF-95 membrane is due to the largely sup­
pressed growth of the undesired nuclei deposition and crystals in the
vapor-assisted growth. The H2 permeance exceeded 7.9 × 10− 7 mol
m− 2 s− 1⋅Pa− 1 which is 4.6 times higher than that of the randomly ori­
ented ZIF-95 membrane. Furthermore, the highly c-orientation
NH2-MIL-125(Ti) membranes were also prepared by combining oriented
seeding and controlled in-plane epitaxial growth [112]. The formation
of the c-orientation membranes results from the oriented seeds layer
interface-assisted self-assembly and single-mode microwave heating
(Fig. 6b). The resultant c-oriented NH2-MIL-125(Ti) membrane had
H2/CO2 ideal selectivity of (number here), 6.1 times as of that the
random oriented membrane and H2 permeance of 4.47 × 10− 8 mol m− 2
s− 1⋅Pa− 1 (133.5 GPU). Recently, the highly (110)-oriented ZIF-8 mem­
branes were further prepared by using a spin-coating method to assist
deposition (110)-oriented seeds layer and secondary growth at a low
temperature (Fig. 6a) which also showed high H2 permeance of ~1.2 ×
10− 7 mol m− 2 s− 1⋅Pa− 1 [113].
H. Lian et al.
Fig. 6. (a) Schematic illustration of preparing highly (110)-oriented ZIF-8 membranes. (b) Procedure for the preparation of highly c-oriented NH2-MIL-125(Ti)
membranes. (c) Schematic illustration of the fabrication of oriented MOF layers (d) Top-view and cross-sectional SEM images of oriented Co-ZIF-67 membrane.
Reproduced with permission from Refs. [112,113,118]. Copyright 2021 Elsevier B.V. Copyright 2018 Wiley-VCH. Copyright 2017 American Chemistry Society.
3.2.3. Nanorods-oriented deposition
The oriented MOF membranes can also be prepared by depositing
metal oxide nanorods combined with solvothermal growth [114,115]. A
new ZIF-8 membrane was successfully prepared by growing seamlessly
of the vertically aligned ZnO nanorods on the support [116]. The ZnO
nanorods were activated to induce a uniform nucleation and guide the
growth of the continuous oriented ZIF-8 membrane. The H2 permeance
exceeded 1 × 10− 6 mol m− 2 s− 1⋅Pa− 1 and H2/CH4 selectivity reached
12.6 which is higher than that of the non-orientated ZIF-8 membrane.
Following this, Li et al. prepared the oriented HKUST-1 and Co3(HCOO)6
membranes by the oriented nano–microstructure assisted controllable
method [117]. The nano-microstructure arrays can directly grow on the
support and penetrate into the formed oriented HKUST-1 membranes,
making the membrane firmly anchored on the support. Thus the H2
permeance of HKUST-1 membrane and Co3(HCOO)6 membrane excee­
ded 2.74 × 10− 6 mol m− 2 s− 1⋅Pa− 1 and 5.25 × 10− 6 mol m− 2 s− 1⋅Pa− 1,
respectively. The high-orientation ZIF-8 and ZIF-67 membranes were
also prepared by using the self-sacrificial template strategy [118]. The
vertically aligned ZnO nanorods were firstly electrodeposited on the
support to guide the subsequent oriented growth of MOF membranes
(Fig. 6c and d), thus enabling the controlled in situ growth of oriented
MOF membranes in a one-pot synthesis. The H2 permeance and H2/CO2
ideal selectivity of Co-ZIF-67 membrane reached ~2.3 × 10− 7 mol m− 2
s− 1⋅Pa− 1 and 7, respectively. The separation performance is superior to
that of non-oriented ZIF-67 membranes.
4. Manipulation strategies for stability
The long-term stability of MOF membrane is another vital property
besides high gas selectivity and permeance. A firm interfacial binding
strength between MOF and support layer plays a key role in improving
MOF membranes stability. Unfortunately, poor heterogeneous nucle­
ation ability of MOF crystals on support surface through direct sol­
vothermal synthesis method is difficult to prepare continuous MOF
membranes with strong interfacial binding strength. Therefore, recent
10
Results in Engineering 15 (2022) 100609
progress to improve the interaction at the boundary of MOF and support
layer is summarized as below. These include support modification
strategy such as organic molecules, inorganic compound functionaliza­
tion of the support and other effective methods.
4.1. Organic molecule modified support
The support can be modified to have active nucleation sites on its
surface by using organic molecules rich functional groups. Simulta­
neously, covalent bonds, hydrogen bonds and van der Waals forces can
be formed between the organic molecules modified support and MOFs
layers resulting a strengthened interacted boundary. Up to now, the
applied organic compounds mainly include silane coupling agent, pol­
ydopamine and so on. For example, Huang et al. applied 3-aminopropyl­
triethoxysilane (APTES) as covalent linker to modify TiO2 support and
prepared continuous ZIF-22 membrane by a solvothermal reaction
[119]. The H2/CH4 separation factor and H2 permeance of the ZIF-22
membrane were 5.2 and 1.6 × 10− 7 mol m− 2 s− 1⋅Pa− 1 at 323 K,
respectively. The ZIF-22 membrane exhibited high thermal stability, and
thus has potential applications in gas separation. Subsequently, a dense
ZIF-90 membrane on APTES modified Al2O3 support was successfully
prepared by the same method [120]. The interface bonding force was
enhanced through the imine condensation between the amine group in
APTES and the free aldehyde group in ZIF-90 framework. Consequently,
the ZIF-90 membrane exhibited excellent separation performance and
stability with H2/CH4 separation factor and H2 permeance of 15.3 and
2.51 × 10− 7 mol m− 2 s− 1⋅Pa− 1, respectively. To evaluate its hydro­
thermal stability, the ZIF-90 membrane was tested to separate an equi­
molar H2/CH4 mixture containing 3 mol % steam at 200 oC and 1 bar.
The ZIF-90 membranes exhibited a reliable stability in the presence of
steam, and both H2/CH4 selectivity and H2 permeance are unchanged
for 24 h. The result shows that the ZIF-90 membrane with hydrothermal
stability combined with its high thermal stability recommends to be
used for H2 purification at high temperatures. Moreover, the 3-(2-imi­
dazolin-1-yl)propyltriethoxysilane (IPTES) was also used as a common
H. Lian et al.
silane coupling agent for support modification [121,122]. Shunsuke
et al. [123] prepared a well-intergrown ZIF-8 polycrystalline membrane
by controlling the graft density of IPTES on α-Al2O3 support (Fig. 7a).
The support surface was rich in imidazole groups because IPTES can
bind to the support through hydrolysis (Fig. 7b). As a result, the imid­
azole groups coordinate with zinc ions or zinc clusters in the solution,
and the initially formed ZIF-8 crystals were fixed on the support
resulting the strong interfacial binding strength.
Inspired by the bioadhesion properties of marine mussels, dopamine
(DPA) can polymerize and adhere on various organic and inorganic
surfaces by forming strong covalent and noncovalent bonds to the sur­
face [124]. Huang et al. [125] modified support by simply soaking the
support into a DPA buffered aqueous solution and prepared a well
intergrown ZIF-8 membrane by a solvothermal method. The covalent
and non-covalent bonds formed between DPA and the initial formed
ZIF-8 enhanced the binding force at the interface. Accordingly, the
H2/CH4 separation factors and H2 permeance reached 31.5 and 1.8 ×
10− 7 mol m− 2 s− 1⋅Pa− 1 at 150 oC and 1 bar, respectively. The ZIF-8
exhibited a reliable stability at high temperatures, which is promising
for H2 purification and separation. On the other hand, MOF membrane
can also be prepared by directly modifying organic polymer as support.
Ammoniation is one of the common ways to modify organic polymer
support. Zhang et. Al [126]. modified organic supports by ammoniating
PVDF hollow fibers in ethylenediamine solution at high temperature and
obtained a continuous NH2-MIL-53 membrane. The resultant amino
groups rich surface and cross-linking between these functional groups
on PVDF hollow fiber lead to high-density active sites support for
NH2-MIL-53 membrane formation. Therefore, the reliable stability was
achieved, and the membranes have big potential in industrial
Fig. 7. (a) and (b) Schematic illustration of the heterogeneous nucleation and crystal growth on the IPTES-grafted surface. (c) Schematic of the all-vapor-phase LIPS
membrane fabrication process. (d) Partial self-conversion of a ZnAl–NO3 LDH precursor layer into a ZnAl–NO3-ZIF-8 membrane. Reproduced with permission from
Refs. [123,131,134]. Copyright 2017 Elsevier B.V. Copyright 2018 American Association for the Advancement of Science. Copyright 2015 Wiley-VCH.
11
Results in Engineering 15 (2022) 100609
application of H2 purification.
4.2. Inorganic compound modified support
The modification of supports with inorganic compounds can provide
additional anchor points for MOF particles initial formation in solution,
hence, increase MOF membranes formability and growth on supports
[127]. Inorganic compounds mainly included metal oxides and layered
double hydroxide (LDH).
These inorganic compounds can directly participate in the reaction
as the metal source and thus penetrate the synthesized MOF membrane,
effectively increase the binding strength between the support and the
MOF membrane. Zhang et al. [128] prepared ultrathin ZnO layer on
Al2O3 hollow fibers surface by slip-casting methods and then activated
the ZnO layer with ligand solution treatment to prepare a continuous
ZIF-8 membrane. The membrane exhibited a reliable stability with high
H2 permeance of 2.08 × 10− 7 mol m− 2 s− 1⋅Pa− 1 and H2/CH4 selectivity
of 10.4. Qiu’s group [129] further prepared continuous ZIF-8 membrane
using ZnO nanorod modified α-Al2O3 ceramic support tube. These ZnO
nanorods can provide abundant nucleation sites for ZIF-8 after being
activated by ligand solution and enhance the binding strength between
ZIF-8 membrane and cambered tubular support. The membrane
exhibited selectively of 9.8 for H2/CH4 and H2 permeance of 1.67 ×
10− 7 mol m− 2 s− 1⋅Pa− 1 at 473 K, indicating the ZIF-8 membranes were
free of defects and stable at a higher temperature. Li et al. [130] suc­
cessfully prepared ZIF-8 membrane by combining methods of sol-gel
coating with vapor deposition. The zinc-based sol was coated on
ammoniated polyvinylidene fluoride support and then the gel layer was
directly converted to a ZIF-8 membrane by ligand vapor deposition. The
H. Lian et al.
H2 permeance and H2/C3H8 selectivity reached 2.15 × 10− 5 mol m− 2
s− 1⋅Pa− 1 and 3400, respectively. It’s worth noting that the gas per­
meances remained largely intact after two measurement cycles of 274 h,
indicating the extraordinary stability. Recently, Tsapatsis et al. [131]
developed an all-vapor-phase method using atomic layer deposition
(ALD) technique to prepare dense ZIF-8 membrane. The ZnO layer was
coated on the active γ-Al2O3 layer by ALD and then was treated by ligand
vapor to transform ZnO into ZIF-8 membranes (Fig. 7c). The membrane
exhibited C3H6/C3H8 separation factor of as high as 152 and C3H6 per­
meance of 3.68 × 10− 8 mol m− 2 s− 1⋅Pa− 1, and remained unchanged for
200 h, which the membrane showed a reliable stability.
On the other hand, the modification of supports through LDH not
only can improve the density of the MOF membrane, but also can
participate in reactions as a metal source to enhance the binding
strength between the MOF membranes and the supports [132]. Caro
et al. [133] utilized ZnAl–CO3 LDH to modify the support surface and
then prepared a high-quality ZIF-8 membrane for gas separation. Sub­
sequently, they prepared the ZIF-8-ZnAl-NO3 LDH composite membrane
by solvothermal treating the ZnAl–NO3 LDH layer on the support with
imidazole ligands [134]. The ligand solution can promote the dissolu­
tion of ZnAl–NO3 LDH and the released Zn2+ ions can coordinate with
the ligand to form a ZIF-8 membrane on the LDH surface (Fig. 7d). The
ZIF-8 layer was firmly attached to the remaining ZnAl–NO3 LDH mem­
brane, which enhanced the interfacial binding strength of the ZIF-8
membrane. The membrane exhibited excellent stability and an
H2/CH4 separation factor as high as 54.1, and the H2 permeance was
about 4.1 × 10− 8 mol m− 2 s− 1⋅Pa− 1.
4.3. Other methods of modifying support
In addition to the above manipulation strategies, other methods can
be used to effectively enhance the binding strength [135]. For example,
Jeong et al. [136] reported the thermal modified support layer by imi­
dazolate ligands resulted in strong covalent bonds/binding strength
between the α-Al2O3 support and imidazole ligand. Hence, it promoted
the heterogeneous nucleation and growth of ZIF crystals. The ZIF-8
membrane exhibited excellent stability with H2/CH4 ideal selectivity
of 13 and H2 permeance of 1.7 × 10− 7 mol m− 2 s− 1⋅Pa− 1. This also
provides a new way to improve stability by enhancing interfacial
bonding. Jin et al. [137] successfully prepared dense Al-MIL-53 mem­
brane on α-Al2O3 support by reactive seeding method. The α-Al2O3
support provided Al source to directly react with ligand solution to form
a uniform and abundant Al-MIL-53 seeds on the support surface, fol­
lowed by soaking into the synthetic solution to prepare Al-MIL-53
membrane. Furthermore, Chen et al. [138] successfully prepared ZIF-8
membrane by hot dip-coating seeding method. The preheated hollow
fiber support was immediately immersed in the suspension of ZIF-8
seeds and the dispersed ZIF-8 crystals firmly embedded in the support
channel under the influence of capillary effect and vacuum force. Thus
ZIF-8 membranes exhibited H2/CH4 ideal selectivity of 10.8 and H2
permeance of 7.29 × 10− 7 mol m− 2 s− 1⋅Pa− 1, and remained unchanged
for 40 h thus, the as-synthesized ZIF-8 membrane has rather good
stability.
5. Challenges and perspectives
In this review, we provide an overview of the main manipulation
strategies to improve gas separation performance of MOF membranes. A
progress based on three characteristics of membrane performance for
gas separation is outlined: selectivity, permeance, and stability. In each
category, the corresponding manipulation strategies and their relation­
ship with gas separation performance are discussed and emphasized in
detail. The aperture/cage precise adjustment and defect elimination in
MOF membrane can significantly improve the gas selectivity but may
affect the gas permeance. Therefore, the introduction of special groups
(e.g., amino and nitro groups or ionic liquids) with strong adsorption (e.
12
Results in Engineering 15 (2022) 100609
g., CO2, hydrocarbons with unsaturated bonds) in this process is a
necessary complementary manipulation strategy. The gas permeance
can be further improved by combining the orientation adjustment and
membrane thickness control. In particular, 2D nanosheet monolayer
membranes with regular channel orientation exhibit both high gas
permeance and ideal selectivity. However, the application range of ul­
trathin membrane is limited by the poor stability under harsh condi­
tions. It is expected that the strong interfacial binding interaction
between MOF and support layer achieved through support modification
can improve the stability of MOF membranes. Therefore, processes to
obtain high purity MOFs nanosheets and monolayer 2D MOFs mem­
branes are the key factors for obtaining high gas separation
performance.
Challenges still remain to achieve a desirable gas separation per­
formance for MOF membranes. A single manipulation strategy cannot
simultaneously improve the selectivity, gas permeance and stability.
Therefore, new simple manipulation or coupled strategies exploration is
highly encouraged. Future directions to improve gas separation perfor­
mance for MOF membrane include: (1) window size and surface
chemistry control in MOF need to be balanced as larger gas molecules
are preferentially adsorbed in the MOF macropores by surface chemical
modification, while non-adsorbed smaller gas molecules pass through
the macropores only through diffusion at a high rate, thus achieving
efficient gas separation. (2) 2D MOFs membranes display superior sep­
aration performances compared with the traditional supported mem­
brane because of the reduction of inter-crystalline defects and the
perfect orientation transport pathways, which is helpful to enhance the
selectivity and permeance. Unfortunately, the preparation of 2D MOFs
membrane is in its infancy. Moreover, the 2D MOFs membrane may be
easily damaged during the actual high-pressure gas separation process,
resulting in an instantaneous disappearance of separation performance.
Therefore, much effort is highly needed to prepare the oriented molec­
ular sieve membranes. The insufficient studies regarding the mechanical
stability improvement for 2D MOFs membrane is another challenge.
Furthermore, reliable MOF membrane materials and novel preparation
methods should also be developed to improve gas separation perfor­
mance, promoting the application of MOF membrane materials in in­
dustry. The MOF membrane formation mechanism should require a
detailed study to guide the scale-up fabrication of MOF membrane areas.
Particularly, retaining the excellent separation performance during the
membranes scaling-up process would be the research focus in the future.
Credit author statement
Haiqian Lian: Methodology, Data curation, Writing – original draft.
Bin Bao: Data curation, Methodology. Jinfeng Chen: Investigation.
Wenhe Yang: Validation. Yu Yang: Visualization. Rujing Hou: Writing
– review & editing. Shengui Ju: Conceptualization, Writing – review &
editing. Yichang Pan: Conceptualization, Supervision.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Key R&D Program of China
(No. 2021YFB3802204), the Natural Science Foundation of China
(21921006, 22022807), the Natural Science Foundation of Jiangsu
Province (BK20200033), and the Priority Academic Program Develop­
ment of Jiangsu Higher Education Institutions (PAPD). Y.P. also thanks
the support from the Six Talent Peaks Project and Qing-Lan Engineering
Project of Jiangsu Province.
H. Lian et al. Results in Engineering 15 (2022) 100609

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