REVIEW
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Lithium Extraction by Emerging Metal–Organic Framework-
Based Membranes
Jue Hou,* Huacheng Zhang, Aaron W. Thornton, Anita J. Hill, Huanting Wang,
and Kristina Konstas*
Lithium is mainly extracted from brine and ores; however, current lithium
mining methods require large amounts of chemicals, discharge many wastes,
and can have serious environmental repercussions. Metal–organic framework
(MOF)-based membranes have shown great potential in lithium extraction
due to their uniform pore sizes, high porosities, and rich host–guest chem-
istry compared to other materials. In this review, the processes and disadvan-
tages of current lithium extraction technologies are introduced. The structure
features and corresponding design strategy of MOFs suitable for Li+ ion
separations are presented. Following, recent advances of polycrystalline MOF
membranes, mixed matrix membranes, and MOF channel membranes for
lithium-ion separation are discussed in detail. Finally, opportunities for future
developments and challenges in this emerging research field are presented.
1. Introduction
Lithium (Li) is the lightest metal on earth. Li is a vital element
due to its diverse applications including Li-ion batteries, glass
and ceramics, lubricating greases, catalysis in polymer and
pharmaceutical production, CO2 absorption materials, and
Al-alloys (Figure  1a). The booming development of Li-ion bat-
teries in smart phones, laptops, portable electronic devices, and
electric vehicles has spawned a strong demand for lithium. The
percentage of global lithium consumption destined for use in
batteries was only 23% in 2010 but has sharply increased to
65% in 2020 (Figure  1b).[1] The global consumption of lithium
content has more than doubled over the past 10 years, from
24.5  kt in 2010 to 56.0  kt in 2020 (Figure  1c), with continued
J. Hou, A. W. Thornton, A. J. Hill, K. Konstas
Manufacturing
Commonwealth Scientific and Industrial Research Organization (CSIRO)
Clayton, Victoria 3168, Australia
E-mail: jue.hou@csiro.au; kristina.konstas@csiro.au
H. Zhang
Chemical and Environmental Engineering
School of Engineering
RMIT University
Melbourne, Victoria 3000, Australia
H. Wang
Department of Chemical Engineering
Monash University
Clayton, Victoria 3168, Australia
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202105991.
DOI: 10.1002/adfm.202105991
Adv. Funct. Mater. 2021, 2105991 2105991  (1 of 14)
growth projected. Lithium naturally exists
in brines, seawater, and mineral deposits.
Although some lithium concentrates such
as α-spodumene can be used directly in
ceramics and glass applications, high
purity lithium production of lithium car-
bonate (Li2CO3) and lithium hydroxide
(LiOH) is necessary to produce batteries.
Current lithium mining processes require
large amounts of chemicals as pro-
cessing aids, discharge large volumes of
waste, and cause serious environmental
impacts. Therefore, it is imperative to
develop cleaner and more efficient lithium
extraction methods to minimize the envi-
ronmental impact, reduce the usage of
chemicals, decrease the amount of waste-
water and waste solids, and lower the energy consumption.
Recently, many novel methods for lithium recovery have
been developed at laboratory scale with the potential for indus-
trial production, such as adsorption–desorption cycling,[2] dif-
fusion dialysis,[3] pulsed electrochemical intercalation,[4] and
membrane separations.[5] The separation processes utilizing
metal–organic framework (MOF)-based membranes have pro-
duced superior results for extracting Li+ from solution.
MOFs composed of metal ions or clusters coordinated to
organic ligands (Figure  2a) have enabled some promising
advances for ion separation applications because they can pro-
vide angstrom-sized porous structures and adjustable host–
guest chemistries between the frameworks and ions. The
geometry and pore size of MOFs, such as ZIF-8,[6] UiO-66,[7]
and HKUST-1,[8] are varied depending on the different types of
crystal structures and their pore size, especially at the subna-
nometer scale, can be precisely manipulated by choosing dif-
ferent ligands.[9] The charge type and charge density of MOFs
also significantly affect the host–guest interaction between
MOFs and ions, resulting in different ion selectivities. They can
be controlled by introducing functional groups via attachment
to the ligands[10] or filling the cavities of frameworks with func-
tional molecules/polymers.[11]
In this review, we briefly introduce current lithium extrac-
tion methods from brine and ores and the present challenges.
The structure features of MOFs suitable for lithium-ion
separations and the corresponding design strategy of MOF
structures are presented. The promising technologies of MOF-
based membrane separation processes and application sce-
narios are also discussed in detail, particularly focusing on the
lithium-ion selectivity and performance of polycrystalline MOF
(PMOF) membranes, mixed matrix membranes (MMMs), and
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Figure 1.  Diverse applications and annual consumption of lithium. a) Various applications of lithium, such as batteries, ceramics, lubricating greases,
air treatment, and catalysis. b) Global lithium consumption by end-use from 2010 to 2020.[1] The ratio of battery-use lithium (red) rises sharply from
2010 to 2021. c) Global consumption of lithium content from 2010 to 2020.[1]
MOF-channel (MOFC) membranes (Figure  2b). We conclude
with ideas for research to meet currently unmet needs.
2. Current Lithium Extraction Methods
2.1. Lithium from Brine
As an active alkaline metal element, lithium exists in the form
of ions in seawater, oil and gas-produced water, and brine
lakes and aquifers. Seawater is a large untapped source of
lithium.[12] Approximately 250 billion tons of lithium are stored
in earth’s seawater.[13] The lithium concentration in seawater is
0.1–0.2 ppm[14] (average 0.17 ppm) with ≈0.1 million tons of sea-
water handled daily by desalination plants globally. Produced
water is also an untapped source of lithium. The concentration
of Li in produced waters varies greatly by region and can range
from 1 to 600  ppm[15] Li (average 44  ppm) with an estimated
45 million tons of produced water handled daily.[16] The concen-
tration of lithium in brine lakes and aquifers varies from 200
to 700 ppm[17] (average 500 ppm) with 0.2 million tons of brine
processed daily. Brine is currently a more practical and com-
mercially viable source of lithium than seawater or produced
water.
Most of the lithium-rich salt lakes are located in the Puna Pla-
teau (on the borders of Chile–Argentina–Bolivia) and Qinghai–
Tibet Plateau of China.[18] A typical brine process involving three
main stages is outlined in Figure  3a. First, brine is pumped
from the lithium-rich saline aquifer and then concentrated by
solar evaporation. Second, Na2CO3 is added to the concentrated
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brine to precipitate Li+ as Li2CO3, a process that also causes
the precipitation of Mg2+ and Ca2+ impurities. Finally, multiple
washing processes are applied to remove impurities and obtain
the end-product—battery-grade Li2CO3 (>99.5 wt%).
The evaporation method is mainly driven by solar energy.
The solar evaporation process presents some disadvantages.
First, the brine of the lithium-rich salt lakes is not surface water
but underground water from saline aquifers. For that reason,
pumping and evaporation may lead to the depletion of the
aquifer. Therefore, the effect of the process on the ecosystem
and geological structures of the salt lakes requires environ-
mental monitoring.[19] Second, the rate of solar evaporation is
determined by the local weather and season, making it a time-
consuming process that can take months to years to achieve.
Third, solid wastes created at the precipitation step are envi-
ronmentally concerning. Fourth, the concentration of Mg2+
in brine, which is much higher than that of Li+, significantly
affects the purification cost for high-purity Li2CO3. Last, the
purification process consumes volumes of fresh water, making
the method water-intensive which is not ideal especially in
regions where fresh water is scarce.
2.2. Lithium from Ores
The other important source of lithium is lithium-containing
ores, such as pegmatites. Pegmatite deposits typically have
large concentrations of lithium-containing minerals, the most
relevant of which is spodumene (LiAl(SiO3)2). The lithium
concentration in the run of mine ores varies from about 0.4 to
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Figure 2.  Structural characteristics of metal–organic frameworks (MOFs) and MOF-based membranes. a) Structure of MOFs and developing directions
of MOFs for mono-/di-valent ion separation (e.g., Li+/Mg2+). MOFs are composed of metal ions/clusters coordinated to organic ligands. To improve the
ion selectivity, pore size, geometry and charge type can be adjusted. By introducing functional groups via attachment to the ligands or filling the cavities
of frameworks with functional molecules/polymers, the charge type of MOFs can be varied from positive to negative. b) Structures of polycrystalline
MOF (PMOF) membrane, mixed matrix membrane (MMM), and MOF-channel (MOFC) membrane.

2.4  wt% Li2O,[20] which is higher than that of brine. This con-
centration renders the lithium extraction process from ores
commercially viable although the approaches are energy-inten-
sive and therefore expensive.
Accessing lithium ions from ores as seen in Figure  3b
requires multistep processing with the formation of both solid
and liquid waste streams. Raw lithium-containing ores, such
as pegmatite, undergo beneficiation which removes impuri-
ties to isolate α-spodumene mineral concentrates.[21] Next, the
natural α-spodumene needs decrepitation at 1050–1100  °C
to phase transform into β-spodumene to improve the solu-
bility of the lithium complexes.[20] Then, β-spodumene will be

Figure 3.  Brief process flow diagrams and disadvantages of current lithium extraction methods from a) brine and b) ores. Red highlight boxes indicate
the disadvantages.

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transformed to soluble salts by acidic or alkaline processes.
For example, β-spodumene can be dissolved in sulfuric acid
at 170–250  °C to form Li2SO4, which can be transformed
to Li2CO3 by adding Na2CO3. In the alkaline process, the
β-spodumene reacts with Na2CO3, NaOH, Ca(OH)2, or lime
under high temperature and high pressure to generate Li2CO3
or LiOH. The LiOH can then be transformed to Li2CO3 in one
more step.
In addition to being energy intensive and expensive, these Li
extraction processes consume large volumes of corrosive chem-
icals, creating large amounts of solid waste in the beneficiation
and alkaline processes, and large amounts of wastewater and
acidic waste in the acidic process, making it difficult to utilize
the waste in an environmentally sustainable manner.
2.3. Summary of Current Extraction, Use, and Reuse
Given the known lithium reserves and the demand projec-
tions, it is possible to estimate peak lithium. Peak lithium is
defined as the point where a peak in production occurs as a
function of time when demand exceeds supply. Peak lithium
without recycling is forecast using various models to occur
in this century between 2074 and 2098.[22] Similar to the work
done to create sustainable scenarios for meeting long-term
demand for other finite resources such as phosphorus,[23]
global lithium security will rest on sustainable lithium meas-
ures that focus research efforts on social and technological
advances in efficiency and reuse. The development of energy
efficient, selective separations technologies will enable effi-
ciency gains in current extraction methods and could enable
viable Li extraction from as-yet untapped sources such as sea-
water and produced water, as well as recovery and reuse of
lithium through recycling, all of which will help achieve global
lithium sustainability.
Figure 4.  The ideal membrane separation process in lithium extraction. a) Schematic illustration of the separation process of a Li+ selective membrane.
Only Li+ can pass through the membrane while Ca2+ and Mg2+ are blocked. b) Routes of membrane separation processes in the Li extraction from brine
and ores. The Li+ is extracted at the permeate side and further transformed to the end-product Li2CO3.
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3. Metal–Organic Framework-Based Membranes
for Lithium Extraction
Membrane technologies have been widely applied in gas sepa-
ration, water treatment, desalination, alcohol dehydration, and
in the dairy industry.[24] Low cost, low energy consumption,
scalability, and high capacity for continuous processing make
membrane separation an attractive field in both fundamental
research and practical application. Ion-selective synthetic mem-
branes have been inspired by the cell membrane with diverse
transmembrane proteins that selectively transport Na+, K+,
Ca2+, and Cl− through the membrane to support life.[25] These
synthetic membranes can be engineered for application in the
mining and resource recovery industries. An ideal schematic
illustration of a membrane-based lithium extraction process
is shown in Figure  4. The membrane selectively permeates
Li+ while blocking other ions (e.g., Ca2+, Mg2+), enabling Li+
to be collected at the permeate side for further conversion into
Li2CO3 by reacting with Na2CO3. Pretreatment, for example,
the removal of large-size impurities, may be necessary. The Li+
can be extracted from Li-rich brine using such a selective mem-
brane, after which the residual Li-poor brine can be injected
back into underground sources thereby avoiding aquifer
depletion. The membrane process can be chemical-free and
continuous, making it attractive from environmental and finan-
cial perspectives. For lithium-rich ores, selective Li+ membranes
can be applied in the acidic processing step of lithium extraction
to reduce the usage of acid for dissolution, alkaline chemicals
for precipitation, and water for purification. Although mem-
branes have been successfully produced for water desalination,
by which all kinds of ions could be moved away from water, the
efficient separation of monatomic ions with the same valence
and similar sizes remains a significant challenge for synthetic
membranes. To achieve single-species selectivity of ions, it has
been recently found that the membranes that have small pores
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comparable to the size of the target ions could achieve high ion
selectivity.[26]
MOFs with subnanometer-size pores provide an ideal
media for construction ion-selective membranes. Although,
MOFs should have no or extremely low electronic conductivity
because they are inorganic–organic hybrid materials and usu-
ally with hydrophobic structure. However, many research works
have shown that MOF materials are excellent ion-conductive
materials due to their high porosity and high-density functional
groups that can be ion carriers in air and water. For example,
MOFs have been widely used for proton conduction,[27] lithium-
ion conduction,[28] and ion sieving,[29] in which MOFs exhibit
potential in the applications of fuel cells, lithium batteries, and
removal of heavy metal ions and anionic species.
The selective ion separation can be classified into two strate-
gies: ion adsorption and ion sieving. Selective ion adsorption
by MOFs has been achieved for radioactive ions (UO22+[30]),
heavy metal ions (e.g., Hg2+,[31] Pb2+,[32] Cd2+[33]), precious ions
(AuIII,[34] PtIV[35]), and toxic oxyanions (e.g., SeO42−, SeO32−,[36]
AsO43−,[37] ReO4−,[38] Cr2O72−[39]) from aqueous solution. The
ion adsorption selectivities of MOFs are sourced from the
host–guest interaction between functional groups on ligands
and ions, such as the specific interaction between SH and
heavy metal ions,[31b] and ion exchanges on ligands or metal
clusters.[40] However, adsorption-based ion-selective separa-
tions require fresh water for desorption and regeneration,
which limits the application in a continuous industrial process.
Ion sieving-type materials, especially MOF-based membranes,
are believed to be a better solution for continuous ion extrac-
tion. The ions are selectively sieved by MOF-based membranes
which are hoped to realize a continuous process and promising
for industrial metal recovery and wastewater treatment.
Considering more than 60  000 crystalline MOF structures
have been developed, for investigating suitable MOFs for Li+
separation by MOF-based membranes, some basic rules are
required to care. First, for Li+ recovery or the separation of mon-
ovalent ions over divalent ions, the pore size of MOFs theoreti-
cally should be under 1 nm because the diameters of hydrated
Li+ and Mg2+ are only 7.64 and 8.56 Å. Besides, the MOFs must
have high stability in water, especially in saline. It has been con-
firmed that MOFs constructed by group IV metals (e.g., Ti, Zr,
and Hf in the +4 oxidation states) and carboxylate-type ligands
have been shown to have high thermodynamic stability in
water.[41] For example, many zirconium-MOFs[42] (e.g., UiO-66
[Figure  2a], UiO-67, MOF-808, and NU-1000) exhibit excellent
water stability especially in acidic solution and weak alkaline
solution, which have been proved when they are applied in the
application of selective ion adsorption. Other types of MOFs,
such as ZIF-8, ZIF-90, MIL-121, and MIL-53, have also been
proved to have certain water-stability. For example, it has been
reported that ZIF-type MOFs are not stable at acidic conditions
but stable at neutral and basic conditions.[6,43] Carboxylate-type
ligand-based MOFs are very stable at acidic conditions, but their
water-stability deceased in water conditions of pH above 10. As
pH values of the ionic solutions are between 5 and 9, most of
the reported water-stable MOFs should be stable enough to do
ion separation experiments in water. They are also promising
in the application of ion sieving membranes. In addition, con-
sidering the positive charge of hydrated metal ions, charged
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MOFs are more promising to achieve high-selective mono-/di-
valent ion separation.
Although developing MOF-based membranes for lithium-
ion separation is quite challenging, some recent surprising
breakthroughs in this field have been reported, which open
pathways for membrane-based metal extraction. Comparing
with the adsorption-based ion separation, besides the chemistry
of MOFs, the membrane structure also plays a significant role
in the sieving performance of MOF-based membranes. There-
fore, we will discuss recent advances in the field of MOF-based
membranes for lithium extraction according to their structural
features and classify these membranes into PMOF membranes,
MMMs, and MOFC membranes (Figure  2b). We identify
common challenges in controlling selective ion binding, sorp-
tion, and diffusion in these classes of membranes and suggest
avenues of research to further optimize performance and lead
to industrial adoption.
3.1. Polycrystalline Metal–Organic Framework Membranes
PMOF membranes have a continuous selective layer of MOF
on porous supports (i.e., nanoporous ceramic, anodic alu-
minum oxide [AAO], and polymeric membranes).[44] They
can be fabricated through a solvothermal method, secondary
growth, contra-diffusion synthesis,[44b,45] and vapor deposition
method.[46] With the growth of knowledge and ability to control
the crystallization of MOFs on porous substrates, it is much
closer to scalably produce PMOF membranes.
The selectivity of PMOF membrane is a result of the MOF
layer, while the porous support only provides mechanical
strength. Therefore, PMOF membranes provide a platform to
investigate the intrinsic properties of MOFs and ion transport
mechanisms occurring in MOF frameworks. In 2018, Zhang
et  al. constructed an ultrathin (<500  nm) ZIF-8 membrane on
AAO substrate and revealed the dehydration–rehydration mech-
anism of ion transport in MOF subnanometer-sized pores.[47]
An electric field (20  mV) was applied as the driving force for
ion transport (Figure  5a). The ion transport ratio can be cal-
culated from ion conductivities reported in I–V curves. The
order of ion transport rate was Li+ < Na+ < K+ < Rb+ when the
ions transported through bare AAO with a pore size of 100 nm
(Figure 5b), while the reverse order of rate Li+ > Na+ > K+ > Rb+
was obtained when they transported through the ZIF-8 mem-
brane. The difference was attributed to partial dehydration
(Figure  5c), where the hydrated ions pass through a pore size
of 3.4 Å within ZIF-8, which is smaller than the hydrated ionic
diameter (dH–Li+ [7.64 Å] > dH–Na+[7.16 Å] > dH–K+ [6.62 Å] > dH–Rb+
[6.58  Å]) but larger than the dehydrated ionic diameter (dLi+
[1.20  Å]  <  dNa+ [1.90  Å]  <  dK+ [2.66  Å]  <  dRb+ [2.96  Å]).[48] The
ions become partially dehydrated as they transport into the
ZIF-8 framework and then rehydrated as they exit, similar to
the process in biological ion channels.[49] The revealed dehydra-
tion–rehydration mechanism of ion transport in MOF subna-
nometer-sized pores provides atheoretical basis for exploration
and explanation of the selective ion transport of MOFs. Mg2+
ions have a larger diameter (1.30 Å fully dehydrated and 8.56 Å
hydrated) and higher hydration energy than Li+;[50] therefore,
there exists a higher barrier to dehydrate Mg2+ and transition
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Figure 5.  Polycrystalline MOF (PMOF) membrane for selective Li+ transport. a) I–V curves of alkali metal ion transport through ZIF-8/GO/AAO
membranes under electric field. b) The hydrated ions pass through a pore directly when the pore size is larger than the diameters of hydrated ions.
c) When the pore size is smaller than the diameters of hydrated ions but larger than the diameters of dehydrated ions, the hydrated ions must partially
dehydrate to enter the pore and rehydrate when they exit. Reproduced with permission.[47] Copyright 2018, AAAS. d) Schematic illustration of the prepa-
ration of a polystyrene sulfonate (PSS) threaded HKUST-1 membrane on AAO substrate. Reproduced with permission.[11a] Copyright 2016, Wiley-VCH.
e) Schematic illustration of the preparation of SSP@ZIF-8 membrane on AAO substrate. The ZIF-8 cage is filled with positively charged zinc hydroxide
nanostrands (ZHNs) and negatively charged sulfonated spiropyran (SSP). The molecular structure of SSP can be reversibly manipulated using light to
realize light-gated cation-selective transport. Reproduced with permission.[11b] Copyright 2020, The Royal Society of Chemistry.

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through the window of ZIF-8. This energy barrier results in a
Li+/Mg2+ selectivity of 45.6.[11b]
In addition to the role of pore size within the framework,
the interaction between the framework and the ions also sig-
nificantly affects the selectivity of PMOF membranes. Intro-
ducing functional groups into the frameworks is an effective
way to enhance the binding affinity between ion and MOF, and
two general strategies have been developed: a) filling the cavi-
ties of frameworks with functional molecules/polymers and b)
attaching functional groups to the ligands. In 2016, Guo et  al.
constructed a polystyrene sulfonate (PSS) threaded HKUST-1
on AAO substrate using an in situ confinement conversion
process (Figure 5d).[11a] Although HKUST-1 has a small pore of
3.5  Å and a large pore of 9  Å (i.e., larger pores than ZIF-8),
a much higher Li+/Mg2+ selectivity of 1815 was achieved. The
Li+ conductivity of this complex membrane (PSS@HKUST-1)
was 5.53  ×  10−4  S  cm−1 at 25  °C, which was five orders higher
than that of the pristine HKUST-1. The sulfonate groups on
PSS dominated the superhigh selectivity of the complex mem-
brane. Notably, PSS also enhanced the stability of the HKUST-1
membrane in water. The PSS@HKUST-1 membrane remained
stable after immersion in water for 2 months. Recently, Liang
et  al. further functionalized a ZIF-8 membrane by filling the
framework with positively charged zinc hydroxide nanostrands
and a negatively charged photoactive molecule, sulfonated spi-
ropyran (SSP), to realize light-gated cation-selective transport
(Figure 5e).[11b] A Li+ conductivity of 1.6 × 10−4 S cm−1 and Li+/
Mg2+ selectivity of 4913 were achieved in a dark environment.
The Li+ conductivity of the SSP@ZIF-8 membrane was higher
than that of the pristine ZIF-8 membrane because the incorpo-
ration of SSP in the membrane efficiently reduced the trans-
port resistances of the cations. The Li+ conductivity reached its
highest value when the SSP doping content was 10% and then
decreased which was attributed to discontinuities and defects
in the membrane. The two isomers of SSP can be used to vary
the Li+ conductivity by a factor of 23, with photoisomerization
effectively acting as an on/off switch. These studies illustrate
the effectiveness of introducing functional groups by filling the
frameworks with functional molecules/polymers for enhancing
the ion selectivity of PMOF membranes.
Introducing functional groups via attachment to the
ligands of the MOF is another strategy to improve ion selec-
tivity. Zirconium MOFs are a class of important candidates
for ion separation due to their excellent water stability and
diversity of ligands.[42a] A variety of UiO-66-type MOFs, such
as UiO-66-NH2, UiO-66-COOH, UiO-66-(COOH)2, and UiO-
66-NO2, have been synthesized using functionalized benzene
1,4-dicarboxylic acid.[10] In 2019, Xu et  al. in situ synthesized
a UiO-66-NH2 membrane on an AAO substrate for cation
separation.[51] Unlike the aforementioned HKUST-1 or ZIF-8
membranes whose surfaces were well-intergrown crystalline
structures (Figure  5d), this UiO-66-NH2 layer exhibited a leaf-
like morphology (Figure  6). This UiO-66-NH2 leaf-like mem-
brane (LLM) had a high cation separation performance for
Na+/Mg2+ > 200 and Li+/Mg2+ > 60.[52] The UiO-66-SO3H LLM
exhibited low Li+/Mg2+ selectivity,[52] with the difference in per-
formance attributed to the functional groups. The diversity of
functionalized ligands provides a promising avenue to precisely
optimize the ion selectivity of PMOF membranes.
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Although several PMOF membranes have been successfully
constructed and exhibited high ion selectivity, some issues still
limit the development of PMOF membranes for ion separation.
To date, only limited kinds of MOFs can be constructed into
defect-free continuous layer due to the difficulty of controlling
crystalline intergrowth. Different from PMOF membranes for
gas separation, some PMOF layer cannot keep highly stable in
aqueous, saline, or various pH environments, so cracks at inter-
growth crystalline interfaces and morphology changes appear
as time goes by which significantly decrease the life of mem-
branes. Even if UiO-66-X MOFs have good water stability, only
several kinds of UiO-66-X of PMOF membranes are achieved
and have ion selectivity.
3.2. Metal–Organic Framework Mixed Matrix Membrane
MOF MMMs employ MOF particles as porous fillers to improve
the selectivity of the polymeric matrix (Figure  7a). Compared
with PMOF membranes, MOF MMMs can be fabricated by
casting the precursor solution of polymer and MOF particles or
by interfacial polymerization,[53] which makes MMMs suitable
for industrial scale-up. Besides, the separated processes of MOF
synthesis and membrane preparation mean MOF particles can
be synthesized under more harsh environments (e.g., higher
temperature, a wider choice of solvents and pH) regarding the
stability of porous substrates and the intergrowth of polycrys-
tals, and more kinds of MOFs can be used. In addition, MMMs
are typically flexible with high mechanical strength, so they can
be rolled for spiral-wound membrane modules.
In 2020, Zhang and coworkers investigated the Li+/Mg2+
selectivity of MOF MMMs by employing six MOFs, including
ZIF-8, UiO-66, UiO-66-SO3H, HKUST-1, MOF-808, and MOF-
808-SO4, as fillers in polyvinyl chloride (PVC) matrix.[54] The
UiO-66-SO3H@PVC membrane exhibited the highest selectivity
(Li+/Mg2+  >  4) among the six MOF membranes (Figure  7b).
The pore sizes of six MOFs are varied from 3.4 to 12.9 Å. UiO-
66-SO3H doesn’t have the smallest pore size but exhibits the
highest Li+/Mg2+ selectivity, indicating the strong interaction
between Mg2+ and sulfonate groups, which could provide nega-
tive charges in a weak alkaline environment. The difference of
Li+ and Mg2+ in the interactions to functionalized MOFs cause
selective transport across the membrane. Notably, this PVC
MMM exhibited low swelling or shrinkage in saline solutions,
and the selectivity of the membrane remained stable for 48 days.
To enhance the connection between MOFs and polymer to
reduce the defects,[55] Xu et al. prepared UiO-66(Zr/Ti)-NH2 by
ion exchange method to replace Zr4+ with Ti3+ to partially neu-
tralize the positive charge and introduce a negative charge in
MOFs and further cross-linked the amino group by trimesoyl
chloride to form thin-film nanocomposite (TFN) layer of MOF/
polyamide on a porous substrate (Figure  7c).[56] The Li+/Mg2+
selectivity of this TFN membrane was 11.38.
Although a variety of MOF MMMs have been developed for
gas separation, water desalination, organic solvent separation,
and chiral separation,[55c,57] the development of MMMs for ion
separation has not proceeded as rapidly, due to the multivariable
multiresponse nature of ion-selective membrane systems. Such
a system is ripe for the application of evolutionary algorithms to
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Figure 6.  UiO-66-NH2 leaf-like membrane (LLM) on AAO substrate for cation separation. a) SEM images of LLM surface (-4s) and cross-sectional (-4c)
morphologies. b) Schematic illustration of a single AAO pore blocked by a UiO-66-NH2 seed and leaves for the sieving of monovalent and divalent
metal ions. c) Schematic illustration of the testing setup for ion selectivity; abbreviations: concentrated, diluted, and electrolyte solutions, AMX = an
anion exchange membrane. Reproduced with permission.[51] Copyright 2019, Wiley-VCH.

speed the optimization of membrane performance.[58] Variables
include polymer matrix charge, water content, free volume size
and distribution, MOF particle size and distribution, ion affinity,
material and process gradients, whilst responses include MOF/
polymer interfacial integrity, polymer swelling and swollen
polymer dielectric constants, and ion transport behavior
(Figure 7a). For example, the ion selectivity of MMMs is attrib-
utable not only to the MOFs but also to the polymer matrix. If
the polymer has high ion conductivity and low ion selectivity,
the ions prefer to transport through the polymer avoiding
the size-selective and affinity-selective attributes of the MOF,
resulting in low selectivity. Alternatively, a polymer with low
ion conductivity will block the ion transport between the MOF
particles, resulting in low flux. The polymer swelling factor in
aqueous environments must be also considered as selectivity
may be reduced. Uniform dispersion and excellent interfacial
compatibilities of the MOF and polymer are highly important.
Voids between the aggregated MOF particles and/or defects at
the MOF–polymer interface provide paths for ion transport that
bypass the selective frameworks, resulting in low ion selectivity.
In addition, operating conditions including pH and salt concen-
tration may induce defects at the MOF–polymer interface. Due
to such a complicated system, to date, the ion selectivity of MOF
MMM is much lower than PMOF membranes.
3.3. Metal–Organic Framework-Channel Membranes
Different from the PMOF membranes and MMMs, a new type
of membrane called MOFC membranes, has been discovered. In
2019, the first MOFC membrane, UiO-66-NH2/polyethylene tere-
phthalate (PET) single-nanochannel membrane, was developed

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Figure 7.  MOF-based MMMs for ion separation. a) Schematic illustration of MOF-based MMMs with ideal structure (left), with varied defects (middle),
and with swollen structure (right). The red balls, blue balls, red lines, blue arrows, and green squares represent Mg2+, Li+, polymeric strands, the
ion transport tracks through MMM, and MOF particles, respectively. b) UiO-66-SO3H@PVC MMM for Li+/Mg2+ separation. Reproduced with
permission.[54] Copyright 2020, Elsevier. c) UiO-66(Zr/Ti)-NH2/polyamide thin-film nanocomposite membrane for Li+/Mg2+ separation. Reproduced
with permission.[56] Copyright 2020, Elsevier.

by Dr. Zhang and Prof. Wang et  al. and it exhibited high
selectivity of F− transport.[59] Subsequently, a series of MOFC
membranes with selective ion transport properties have been fab-
ricated and systematically investigated.[60] A barrier polymer (e.g.,
PET) with nanochannels is employed as the support, and the
PMOF-filled nanochannels provide the only path for ion trans-
port. Such MOFC membranes can combine both the flexibility of
polymeric membranes and the high selectivity and permeability
of MOFs, and they can avoid the swelling effect in MMMs due
to the barrier polymer is non-swollen and non-permeable. As a
brand-new field, the current fabrication methods of MOFC mem-
branes are only interfacial synthesis or solvothermal method. The
performance of MOFC membranes is controlled by the intrinsic
properties of the MOFs (e.g., pore size, affinity between MOFs
and ions), various defects (between MOF crystals and at the inter-
face of MOFs and the polymeric channels), and features of the
polymeric nanochannels (shape, size, channel density, etc.). The
MOFC membrane provides a novel platform for the fundamental
investigation of ion transport through MOFs.
Recently, they reported a bullet-shaped PET single-nano-
channel membrane filled by UiO-66-(COOH)2 which achieved
highly selective separation of mono-/di-valent ions (Figure 8).[61]
An optimized selectivity of 1590 for Li+/Mg2+ (0.1 m under a 1 V
driving force) was achieved. Computational simulations indi-
cated that the interactions between the ions and the carboxylic
groups of UiO-66-(COOH)2 lowered the energy barriers for
monovalent metal ions to transport through the MOFC mem-
branes, resulting in the ultrahigh selectivity. The carboxylic
groups on PET, created during the chemical etching process,
were important for bonding at the interface between UiO-66-
(COOH)2 and the polymeric channels. Although there was only
one nanochannel on this MOF single-nanochannel membrane

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Figure 8.  MOF channel (MOFC) membrane for mono-/di-valent metal ion separation. a) UiO-66-(COOH)2 crystalline structure with tetrahedral and
octahedral cavities (≈8–11  Å in diameter) connected by angstrom-sized triangular windows (≈6  Å in diameter). b) Bullet-shaped PET nanochannel
with UiO-66-(COOH)2 at tip side. This MOFC membrane exhibits high conductivity of Li+ over Mg2+. c) Ion selectivity of UiO-66-(COOH)2-single-
nanochannel membrane as a function of ion concentration. Reproduced with permission.[61] Copyright 2020, Nature Publishing Group.

resulting in low flux of the whole membrane, the flux can be
significantly improved by simply increasing the channel den-
sity of the membrane from a single nanochannel to multina-
nochannels (such as 105 cm−2 or higher). This work gives new
inspiration for designing and scaling MOF multinanochannel
membranes for lithium-ion extraction. Recently, they further
grew UiO-66-COOH in PET single-nanochannel membrane
to investigate the ion transport property.[62] As the decrease of
COOH density comparing to UiO-66-(COOH)2, more space
will be there in the window of the framework for ion transport,
resulting in higher ion conductivity of the MOFC membrane
and lower mono-/di-valent ion selectivity (≈200 for Li+/Mg2+).
This result also indicated the influence on ion selectivity of
MOF by the charge density.
Besides the functional groups of UiO-66-(COOH)2, the struc-
ture of the MOFC membrane also contributes to the selective
ion transport. Comparing with the ones of PMOF membranes,
no defect-free continuous MOF layer is required to be synthe-
sized and the MOF crystalline interfaces of MOFC membranes
are obviously reduced, so the difficulty of the preparation of
MOFC membranes is much lower. Some MOFs, which could
not be synthesized into a continuous layer of PMOF membranes
(e.g., UiO-66-(COOH)2[61] and UiO-66-COOH[62]), can be synthe-
sized into the nanochannels as MOFC membranes by interfacial
synthesis. Besides, some reactions and functionalizations can
also be achieved on the MOFs of MOFC membrane to realize
different ion selectivities without destroying the uniform MOF
structure.[59,60] Furthermore, the MOFCs also provide more
adjustable parameters, such as symmetric or asymmetric shapes
of nanochannels,[63] to gain extra features of membranes, such
as ionic current rectification.[60b] In addition, such MOFC mem-
branes are also flexible as MMMs, so they have great potential to
be compatible with current spiral-wound membrane modules or
flat sheet membranes for industrial applications.
4. Conclusions
In this review, the current lithium extraction methods are briefly
introduced and recent advances in MOF-based membranes for
lithium-ion separation are summarized including PMOF mem-
branes, MMMs, and MOFC membranes. Both the intrinsic
properties of MOF materials and the structural features of
MOF-based membranes significantly affect the ion separation
performance of membranes. As shown in Table  1, which has
summarized the data of reported MOF-based membranes for
mono-/di-valent ion separations sorted as the increasing pore
size of MOF, no ion conductivity can be measured for ZIF-7
whose pore size was only 2.9 Å, while only low selectivity can be
achieved when the pore is larger than 10 Å. Besides, comparing

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Table 1.  Summary of MOF-based membranes for mono-/di-valent ion separation.

MOF membranes Pore Size [Å] Functional Group Charge Type Membrane Type Ion Selectivity Ref.
+ 2+ + 2+ + 2+ + +
Li /Mg Na /Mg K /Mg Li /K
ZIF-7 2.9 — Neutral MOFC — — — — [5a]
ZIF-8 3.4 — Neutral PMOF 3.87 4.0 4.49 0.86 [66]
ZIF-8 3.4 — Neutral PMOF — — 2.18 [5a]
ZIF-8-SSP 3.4 SO3− Negative PMOF 4913 64 44 112 [11b]
ZIF-8@PVC 3.4 — Neutral MMM 2.02 1.51 1.71 1.18 [54]
UiO-66 6 — Neutral MOFC — — — 1.58 [5a]
UiO-66@PVC 6 — Neutral MMM 1.30 1.55 1.83 0.71 [54]
UiO-66-NH2 6 NH2 Positive PMOF (LLM) >60 — — — [51]
UiO-66-SO3H 6 SO3− Negative PMOF (LLM) 1.88 — 5.31 0.35 [52]
UiO-66-SO3H@PVC 6 SO3− Negative MMM 4.79 5.15 5.99 0.80 [54]
UiO-66(Zr/Ti)-NH2@Polyamide 6 — — MMM 11.38 13.44 — — [56]
UiO-66-(COOH)2 6 COOH/COO− Negative MOFC 1590 3230 4948 0.32 [61]
UiO-66-COOH 6 COOH/COO– Negative MOFC ∼200 — 1554.9 — [62]
HKUST-1-PSS 9 SO3− Negative PMOF 1815 52 27 67 [11a]
HKUST-1@PVC 9 — Neutral MMM 1.27 1.59 2.00 0.64 [54]
MOF-808-SO4@PVC 12 SO4 — MMM 1.06 1.20 1.51 0.70 [54]
MOF-808@PVC 12.9 — Neutral MMM 0.79 1.04 1.32 0.60 [54]

with MOFs without functional groups, functionalization of
MOFs with molecules of cation-binding groups could further
enhance the membrane selectivity. Therefore, to further develop
MOF-based membranes for lithium extraction, the MOF should
have pore size of 3–10 Å and cation-binding functional groups.
For the MOFs with similar pore sizes, such as UiO-66-X
series, the PMOF and MOFC membranes could achieve orders
of magnitude higher ion selectivity of the MMMs, which indi-
cates the importance of membrane types. The fabrication
methods, structural features, defects source, and scalabilities of
each kind of membranes are summarized in Table 2. The mem-
brane structure decided the applications and scalability of dif-
ferent MOF-based membranes. Considering the broader choice
of MOFs, high flexibility, and good scalability to spiral-wound
membrane modules which could be connected with current
water treatment system, developing MMMs and MOFC mem-
branes with high selectivity will become a research hot spot of
this field in near future.

Table 2.  Summary of different types of MOF-based membranes.

Membrane Source of Selectivity Fabrication Method Flexibility Choice of MOFs Defects Source Permeance Selectivity Scalability
Type
PMOF MOF 1. Solvothermal method No Limited 1. Interface of inter- High High 1. Flat sheet
Membranes 2. Secondary growth grown MOF crys- membranes
3. Contra-diffusion syn- tals 2. Hollow fiber
thesis 2. Cracks induced by membranes
4. Vapor deposition saline environment
method and pH
MMMs MOF & polymer 1. Casting Yes Unlimited 1. Interface of poly- Low Low 1. Spiral-wound
2. Interfacial polymeriza- mer and MOF par- ­membrane
tion ticles modules
2. Voids between ag- 2. Hollow fiber
gregated MOF par- membranes
ticles 3. Flat sheet
3. Polymer swelling membranes
and swollen
MOFC MOF 1. Interfacial synthesis Yes Broad 1. Interface of inter- Depending on High 1. Spiral-wound
Membranes 2. Solvothermal method grown MOF crys- pore density of ­membrane
tals polymer support modules
2. Interface of MOF 2. Flat sheet
and polymer chan- membranes
nels

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www.advancedsciencenews.com
To date, the lab-scale MOF-based membranes show good
selectivity for Li+/Mg2+ in aqueous solution and exhibit scale-
up potential for industrial lithium extraction. The durability
of these membranes in high fidelity operating conditions still
needs to be tested. There are several promising directions in
this attractive research field waiting to be further explored. Ion
selectivity has been shown to be governed by the membrane
material characteristics, and further work is needed to extend
the performance to continuous processes for resource recovery
from sea water, brine, mineral processing streams, processing
waste waters, produced water, and recycling processes. For
example, a deeper understanding of the interaction between
the hydrated ions and the functional groups of MOFs (and poly-
mers for MMM) is needed. From the studies to date, functional
groups can exhibit a stronger influence on the selectivity and
conductivity than the geometry of the frameworks. The inter-
play between solubility and diffusivity effects must continue to
be optimized. In silico design coupled with systematic materials
synthesis and testing will guide such performance optimization.
For MOFC membranes, the influence of the shape and surface
chemistry of the nanochannel needs to be systematically inves-
tigated. Previous studies of PET nanochannels with different
shapes and functional modifications have found significant
differences in mass transport, resulting in varied gating, recti-
fication, and sensing properties.[63a,64] By optimizing the shape
and functionality of polymer channels, higher performance of
these MOFC membranes can be achieved. Advances in the fun-
damental understanding of ion transport through MOF frame-
works, including computational simulation to predict and guide
membrane design,[65] will facilitate the development of MOF-
based membranes for practical ion separations.
Acknowledgements
The authors appreciate the financial support from CSIRO Manufacturing
and CSIRO Research Office.
Conflict of Interest
The authors declare no conflict of interest.
Keywords
ion selectivities, ion transport, lithium extraction, membranes, metal–
organic frameworks
Received: June 21, 2021
Published online:
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www.advancedsciencenews.com www.afm-journal.de

Jue Hou is currently a postdoctoral fellow at the CSIRO. He received his B.S. degree in materials
chemistry at Peking University in 2011 and Ph.D. degree in Materials Science at the Institute of
Chemistry, Chinese Academy of Sciences (ICCAS) in 2016 under the supervision of Prof. Yanlin
Song. Then, he worked as a postdoc in Prof. Huanting Wang’s group at Monash University to
develop porous membranes composed of MOFs and carbon molecular sieves for gas and ion
separations. From June 2019, he joined CSIRO to further develop MOF-based membranes for
industrial applications under the supervision of Dr. Kristina Konstas.

Huacheng Zhang is currently a senior lecturer and ARC future fellow in the chemical and envi-
ronmental engineering at RMIT University. She received her Ph.D. degree in physical chemistry
from Prof. Lei Jiang’s group at ICCAS in 2014. Then, she worked as an assistant professor at the
Technical Institute of Physics and Chemistry, CAS and a postdoc research fellow and an ARC-
DECRA Fellow in the Department of Chemical Engineering at Monash University. Her current
research interest focuses on bioinspired smart ion channel materials, nanofluidics, and MOF
channel membranes for efficient separation applications.

Aaron W. Thornton is currently a senior research scientist at the CSIRO. He received a B. Math
(Fin) in 2005 and completed a Ph.D. in mathematical modeling in 2010 at the University of
Wollongong. He then went to build the Virtual Screening Platform at the CSIRO as an office of the
chief executive postdoctoral fellow to accelerate the atomistic design of advanced porous mate-
rials. After 10 years, his capability has led to both fundamental and commercial breakthroughs in
efficient separations using MOFs, including Airthena for direct air capture of trace components.

Kristina Konstas is currently a senior research scientist at the CSIRO after joining the organization
in 2010 as an office of the chief executive postdoctoral fellow. She completed her Ph.D. in organo-
metallic chemistry from Monash University (Australia) in 2007 under the supervision of Prof. G. B.
Deacon and Prof. P. C. Junk. Her current research interests focus on the development of porous
materials for the direct capture of carbon dioxide from air. Other research interests include porous
composite developments for lithium adsorption, separation, and toxic gas capture.

Adv. Funct. Mater. 2021, 2105991 2105991  (14 of 14) © 2021 Wiley-VCH GmbH