1 s2.0 S0048969721047379 Main

Science of the Total Environment 800 (2021) 149662
Contents lists available at ScienceDirect
Science of the Total Environment
journal homepage: www.elsevier.com/locate/scitotenv
Recent advances in metal-organic framework membranes for water

treatment: A review
Shujun Yu a,b, Hongwei Pang b, Shuyi Huang b, Hao Tang b, Shuqin Wang a, Muqing Qiu a, Zhongshan Chen b,
Hui Yang b, Gang Song d, Dong Fu c, Baowei Hu a,⁎, Xiangxue Wang c,⁎
a
School of Life Science, Shaoxing University, Shaoxing 312000, PR China
b
MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, PR China
c
Hebei Key Lab of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, PR China
d
Guangdong Provincial Key Laboratory of Radionuclides Pollution Control and Resources, School of Environmental Science and Engineering, Guangzhou University, Guangzhou 510006, China
H I G H L I G H T S G R A P H I C A L A B S T R A C T
• The developmental timeline of MOFs-

containing membranes for water treat-
ment are summarized.
• The synthesis strategies of various
MOFs-containing membranes are intro-
duced.
• The removal performances of MOFs-
containing membranes for various pol-
lutants are determined.
• The mechanisms mainly ascribe to size-
exclusion, π-π stacking interaction, elec-
trostatic interaction, hydrogen bonding.
• Multi-factor influences demonstrate the
practical application potential of MOFs-
containing membranes.
a r t i c l e i n f o a b s t r a c t
Article history: Among many separation membranes reported to date, the favorable polymer affinity and unique physio-
Received 6 April 2021 chemical performances of metal-organic frameworks (MOFs) including ultra-high surface area, regular and
Received in revised form 16 July 2021 highly controlled porosity have drawn widespread attention in industrial and academic communities. In this
Accepted 10 August 2021
comprehensive review, the developmental timeline of MOF containing membranes for water treatment were
Available online 13 August 2021
clarified. The removal efficiencies, elimination mechanisms, as well as possible influencing factors of various
Editor: Baoliang Chen MOF containing membranes that applied to water treatment were systematically summarized. The excellent
removal performances of MOF containing membranes for various pollutants were determined by the size-
exclusion, π-π stacking interaction, electrostatic interaction, hydrogen bonding and so on. Since the progress of
Keywords: engineered MOF containing membranes for practical wastewater treatment applications lags, we further ana-
MOFs lyzed the potential environmental application of MOF containing membranes from four aspects (stability of
Membranes MOFs, antifouling performance of membranes, compatibility between MOF fillers and polymer matrix, dispersity
Water treatment of MOF nanoparticles in matrix), hoping to provide some meaningful insights.
Stability
© 2021 Elsevier B.V. All rights reserved.
Antifouling
Compatibility
⁎ Corresponding authors.
E-mail addresses: [email protected] (B. Hu), [email protected] (X. Wang).
https://doi.org/10.1016/j.scitotenv.2021.149662
0048-9697/© 2021 Elsevier B.V. All rights reserved.
S. Yu, H. Pang, S. Huang et al. Science of the Total Environment 800 (2021) 149662
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.1. Advantages and limitations of MOFs. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2. Water treatments by MOF containing membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.3. The purpose of this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2. MOF containing membranes for water treatment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.1. Oily and micro-pollutant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
2.2. Organic dye waste decontamination. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
2.3. Heavy metal ions uptake . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.4. Brackish water and seawater desalination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3. Environmental application assessment of MOF containing membranes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.1. Stability performance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
3.2. Antifouling characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.1. High surface hydrophilicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.2. Low surface roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
3.2.3. Negative surface charge . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3. Other properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3.1. Compatibility between MOF fillers and polymer matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.3.2. Dispersity of MOF nanoparticles in matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
4. Conclusions and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
Declaration of competing interest. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1. Introduction Despite the great advantages of MOFs summarized above, there are
some limitations for applications of powdered materials in environmen-
1.1. Advantages and limitations of MOFs tal governance as well, including (Bétard and Fischer, 2012; Kadhom
and Deng, 2018; Li et al., 2020; Li et al., 2017a): (I) the nanoscale size
Metal-organic frameworks (MOFs) represent an exciting novel type of powdered MOF makes it easy to aggregate and then led to blocking
of nanoporous inorganic-organic hybrid materials with one- troubles in water treatment, which will produce secondary pollution
dimensional, two-dimensional, or three-dimensional topological struc- and reduce the adsorption efficiency; (II) powdered MOFs are suscepti-
ture that formed by connecting inorganic metal ions or clusters with or- ble to be consumed in practical applications, which reduced the service
ganic ligands. As one of the most promising functional nanomaterials, life and increased the operating costs; (III) synthesis of multi-functional
MOFs show superior potential in liquid separation, luminescence sens- MOFs with controllable size/shape as well as excellent selectivity is
ing, gas storage, drug delivery, catalysis, and have numerous advantages relatively complex, and the large-scale production of low-cost MOFs
for environmental remediations such as (Cheng et al., 2021; Li et al., for industry applications still needs much effort to develop; and (IV)
2018b; Liu and Wöll, 2017; Liu et al., 2021a, 2021b; Wang et al., large-scale industrial applications are limited by immature production
2019a): (1) Highly crystalline solid compounds. MOF is a solid com- methods, uncertain cycle life, and unstable biocompatibility. To fully ex-
pound with high crystallinity, which is conducive to the confirmation ploit the excellent characteristics of MOFs and overcome the problems
of its precise space structure via single/poly-crystal diffraction; that may exist in practical applications of powdered MOFs, MOFs are
(2) Large porosity and specific surface area. Due to the long ligands, usually deposited on polymer matrix to form membranes, and thus to
MOFs possess large specific surface area (~ 7140 m2/g) and high poros- overcome the regeneration problem and potential safety concerns as-
ity (~ 94%), which are much higher than other porous materials; (3) Di- cribe to undesirable leakage.
versity and adjustability of the structure. The structural units of MOF can
be combined by different metal ions/clusters, bridging ligands and dif- 1.2. Water treatments by MOF containing membranes
ferent coordination structures through coordination bonds, thus its
structure is diversiform. Speculatively, MOF-based composites with It is universally accepted that the industrialization and urbanization
specific frame structures can be fabricated by rational monomer design not only promote global economic growth, but also bring heavy
and synthetic assemble; (4) Unique functionality caused by flexibility. resource and environmental costs to humanity. Among them, the
The organic ligands that constitute MOFs are usually long and have σ- worldwide water shortage that caused by the rapidly increasing popu-
bond. And the common coordination bonds are also like σ-bonds, lation and severe water contamination, is one of the most serious and
with the characteristics of reversibility and deformability. Therefore, longest-term problems that facing the international community in the
MOFs are mostly flexible, while the traditional porous materials of inor- 21st century (Hao et al., 2021; Yao et al., 2021). Water treatments,
ganic molecular sieves do not possess that. In addition, the flexibility of such as oily and micro-pollutants removal, organic dyes' waste
MOFs can bring some peculiar properties, for instance particular physi- decontamination, heavy metal ions' uptake, brackish water and
cochemical changes and multi-step adsorption/desorption processes; seawater desalination, has been considered as feasible strategies to
(5) Rich in physical and chemical functions. Porous MOFs possess pure solve this major challenge, which has attracted extensive attention in
organic or organic-inorganic hybrid porous surface, thus showing mul- academia (Fang et al., 2021; Li et al., 2021; Qiu et al., 2021; Wu et al.,
tifarious surface physical and chemical functions, and endowing MOFs 2019). To date, as a rapidly emerging separation and purification
potential abilities; and (6) Easy modifiability. The reversibility of technology, membrane separation technology has been widely applied
MOFs' coordination bonds and the functionalization of organic ligands in water pollution remediations due to the selective separation
enable the metal center and organic ligands of MOFs to change the performance, strong adaptability, easy maintenance, small footprint,
structure, while the framework and pore surface can be functionalized and high efficiency characteristics (Li et al., 2020; Wang et al., 2019a;
through chemical modification. Zhu et al., 2017b). With the unique advantages of MOF and membrane
2
separation technology, MOF containing membranes have become a new MOF containing membranes for separation on multiple inorganic sam-
candidate as water treatment membrane. It is formed by continuous ples through different methods. While Stage-2 was related to the prep-
growth of specific polycrystalline MOF layers on polymer substrates, aration of MOF containing membranes with excellent performance and
and the substrates can provide strong mechanical strength for mem- their applications in the fields of wastewater remediation, desalination,
branes while applications. Since they were successfully prepared in selective ions separation, etc. Specifically, in 2012, the bare ZIF-8 mem-
2005 (Hermes et al., 2005), their characteristics of regular and tunable brane used for propane/propylene organic mixtures separation was
porosity, excellent selectivity and permeability, better compatibility synthesized by Pan et al. (2012), which manifested the long-term stabil-
among polymers, made them own potential value in practical water ity and excellent reproducibility of MOF membranes. Subsequently, the
remediations. pure UiO-66 polycrystalline membranes that built on alumina hollow fi-
Fig. 1 illustrates some developmental timelines of MOF containing bers were used for desalination (Liu et al., 2015b). Meanwhile, a series
membranes for water treatments. Briefly, the applications of MOF con- of MOF containing mixed-matrix membranes (MMMs) fabricated on
taining membranes for water treatments can be divided into Stage-1: different substrates were also successfully formed and used for the se-
tentative researches (from 2005 to 2009); Stage-2: rapid developments questration of mixed dye solutions (methyl orange/Coomassie blue)
(from 2010 to 2020); Stage-3: future challenges (from 2021 to future). (Denny and Cohen, 2015). In 2018, a novel PAA/ZIF-8/PVDF (poly(vinyl-
And the focus of Stage-1 was to investigate the preparation of available idene fluoride) (PVDF), polyacrylic acid (PAA)) hybrid ultrafiltration
First MOF membranes

applied in (gas) separation
Micropor. Mesopor. Mat., 2009, 118: 296-301
First MOF membranes

prepared by microwave on polymer substrate
First bare MOF J. Am. Chem. Soc., 2010, 132: 15687-15691
(MOF-5) membranes
J. Am. Chem. Soc., 2005,
127: 13744-13745 Bare ZIF-8 membrane used for
organic separation
J. Membr. Sci., 2012, 390-391: 93-98
First MOF membranes applied
in catalysis;
Bare MOF membranes obtained Bare MOF membrane fabricated
through secondary-growth method by direct-growth on unmodified
substrates
Appl. Catal. A: Gen., 2011, 391:261-267
Chem. Commun, 2013: 10569-10571
Chem. Commun., 2011, 47: 737-739
Bare MOF membrane used for desalination;

MOFs nanosheets first as
Separation of mixed dye solution was
building blocks for molecular
realized by MOF membranes
sieving membranes
Science, 2014, 346: 1356-1359 J. Am. Chem. Soc., 2015, 137:6999-7002
Angew. Chem. Int. Ed., 2015, 54: 9029-9032
Explored the effect of MOFs The effects of the chargeability

layer thickness on water flux of MOF membranes on the
of MOF membranes retention of dye and the water
ACS Appl. Mater. Interfaces, 2016, 8: flux were studied
21979-21983 J. Mater. Chem. A, 2017, 5: 15342-15355
MOF hybrid UF membrane firstly Thin-film composite membrane with

used for removing trace Ni(II) in interlayer decorated UiO-66 toward
high salinity industrial wastewater enhanced forward osmosis performance
Water Res., 2018, 143: 87-98 Ind. Eng. Chem. Res., 2019, 58: 195-206
Novel high-flux positively charged

MIL-125(Ti) membranes for heavy
metal removal
Chem. Eng. J., 2020, 398: 125706 Future
Fig. 1. A developmental timeline of MOF containing membranes for water treatments (Centrone et al., 2010; Denny and Cohen, 2015; Gong et al., 2020; Hermes et al., 2005; Hu et al.,
2011a; Kang et al., 2013; Li et al., 2018c; Liu et al., 2015b; Liu et al., 2009; Pan et al., 2012; Peng et al., 2014; Ramos-Fernandez et al., 2011; Wang et al., 2016b; Wang et al., 2019c;
Yang et al., 2017a).
3
(UF) membrane was fabricated and exhibited the highest removal have been extensively explored in removal of oily wastewater
efficiency of Ni(II) (up to 219.09 mg/g) even in high‑sodium solution (Table 1). The MOF membranes with different affinity for the oil/
(CNa+ = 15,000 mg/L) was reported, which marked a major challenge water phase on the surface can realize selective oil-water mixture. The
of removing trace heavy metal ions from high-salt wastewater has super-hydrophobic and super-lipophilic properties of membranes to-
been overcome (Li et al., 2018c). Very recently, the research hotspots ward the oily wastewater can be enhanced through the synergistic ac-
of MOF containing membranes in water treatments are to fabricate tion between super-wettability and abundant porosity (Goh and
high-quality and stable membrane through selecting the appropriate Ismail, 2018). As shown in Fig. 2A, Gu et al. (2019) fabricated a super-
fabricated methods, adjusting structural characteristics, as well as mod- hydrophobic/super-lipophilic ZIF-8@rGO@Sponge membrane by im-
ifying the membrane surface, and to extend their application areas bedding MOF nanomaterials among GO nanosheets then by a high-
finally. temperature reduction self-assembly. The ZIF-8@rGO@Sponge showed
high sorption selectivity for oils with ultrahigh separation efficiency
1.3. The purpose of this review (˃98%) due to the synergistic effect. Moreover, the composite membrane
kept excellent removal efficiency for oils even after 100 cycles, demon-
The development of advanced MOF containing membranes is crucial strating its outstanding recyclability. Taking into account the higher re-
to resolve the global challenges of aquatic environment pollution and moval capacity, stronger selectivity, and good recyclability, the ZIF-8@
water scarcity. In this context, a number of MOF membranes-related re- rGO@Sponge not only provided promising materials for water-oil sepa-
views focusing on fundamental theories, physicochemical properties, ration and wastewater disposal, but also provided a new concept for the
synthetic routes, and diversified applications were published, which development of MOF containing membranes. Additionally, given the
reflected the substantial attention received by researchers (Deng et al., fact that the oil wettability properties of MOF containing membranes
2021; Li, 2019; Liu et al., 2020). Li (2019) reported the various synthesis can be also enhanced through controlling the diameter and the surface
strategies which could improve the quality and applicability of MOF of MOF nanoparticles, Xiu et al. (2016) incorporated ZIF-8 nanoparticles
membranes, accompanied with their potential applications. Liu et al. into the poly (lactic acid) (PLA) to fabricate the PLA/ZIF-8 composite
(2020) concentrated on the fabrication of MOFs membranes and their electro-spun membranes and applied it in oil/water separation. The
applications in electrocatalytic. Deng et al. (2021) mainly introduced roughness of the membrane was enhanced, and the diameter of blend
the design strategies and latest applications of MOF-based membranes fiber was reduced with the increasing of ZIF-8 nanomaterials content
in oil-water separation. Recently, in view of the rapid development of in membranes. Moreover, the contact angle test also confirmed that as
MOF-based membranes and so as to uncover the full potential in the ZIF-8 content increased, the diffusion time of saxoline droplets on
water resources regeneration and wastewater treatment, Li et al. the PLA/ZIF-8 composite membrane was obviously shortened, which
(2020) paid special attention to the current challenges and proposed fu- was mainly due to the significant improvement of the oil wettability
ture research directions. Although these excellent reviews are of great of membrane. Based on the roughness, wetting ability, and the adsorp-
reference significance, reviews aimed at the challenges in practical ap- tive action of polyporous ZIF-8 nanomaterials, when the oil/water mix-
plications, the solutions to these challenges, and the possible environ- ture was poured on the PLA/ZIF-8 membranes, the oil globules soaked
mental applications of MOF containing membranes are still required, the membranes quickly and were assimilated by the membranes
which are significant for MOF containing membranes to move from the- while the water molecules pass through the membranes (Fig. 2B),
oretical research to applications. which endowed the membrane a high separation efficiency for diesel/
In this review, we firstly summarized the applications of MOF con- water separation.
taining membranes in water treatments involving the key performance, Compared with conventional oil-water separation membranes
influencing factors and mechanisms. Subsequently, the stability proper- (such as polymer membranes, ceramic membranes, zeolite membrane
ties, antifouling characteristics, compatibility, and dispersity involved in and graphene oxide membranes), MOF membranes presented excellent
the environmental applications are highlighted. Ultimately, we propose selectivity, permeability as well as chemical stability (Deng et al., 2021).
a few perspectives on the future research focus of MOF containing In addition, the main mechanisms of oil-water separation by MOF mem-
membranes for large-scale commercial applications. We believe that branes were hydrophilic interaction and size-exclusion. However, the
this review will be a bonanza for investigators to obtain a deep under- problems including low membrane fluxes, high preparation costs, and
standing of the inevitable connections between performance and appli- membrane fouling still need to be resolved in the applications of oil-
cation, as well as strategies for the fabrication and preparation of MOF water separation. Therefore, future investigation on MOF membranes
containing membranes with high quality in environmental in oily wastewater removal will concentrated on the design and fabrica-
managements. tion of low-cost MOF membranes with high separation efficiency, high
permeation, and flux excellent antifouling properties.
2. MOF containing membranes for water treatment Besides oil contaminants, micro-contaminants (for instance, phar-
maceuticals, endocrine disrupters, and personal care products, pesti-
The adjustable compositions, controllable structures, and excellent cides, and polycyclic aromatic hydrocarbons) also bring severe water
separation performances of MOF containing membranes make them pollutions even at low concentration. In recent years, the intercalation
promising scavengers for water pollution control, such as the removal of MOFs into the polymeric substrate to fabricate multi-functional
of oily and micro-pollutants, the elimination of heavy metal ions, the de- membrane materials presents a probability for efficient elimination of
contamination of organic dye, as well as the desalination of brackish micro-pollutants based on the strong complexing ability of MOFs
water and seawater. In this chapter, the representative applications of (Table 1). For instance, Ragab et al. (2016) functionalized the
MOF containing membranes in water treatment are exhaustive polytetrafluoroethylene (PTFE) bilayer filter membrane with ZIF-8 and
discussed and highlighted in Tables 1–4. applied it for the elimination of progesterone. In contrast to the pure
membrane material, the adsorption capacity of MOF containing com-
2.1. Oily and micro-pollutant removal posite membrane increased about 40%. In addition, the removal effi-
ciency of MOF containing composite membrane remained as high as
Oil pollutions, always derived from the textile, steel, and petroleum 95% even after three regenerative cycles by using hormone with high
industries, as well as the frequent oil leakage accidents during oil concentrations. Notably, the enhancement of the membrane elimina-
exploitation or transportation, have become a worldwide environmen- tion capacity was mainly because the increasing of the effective contact
tal issue. Credited with the excellent properties and the fact that MOFs area and the hydrogen bond interaction between the ZIF-8 (hydrogen
can be easily fixed onto membranes, MOF containing membranes donor) and hormone (hydrogen acceptor). Moreover, Dai et al. (2019)
4
Table 1
Oily and micro-pollutant removal on MOF containing membranes.
Targets Membranes Key performance Mechanisms Influence factors Ref
Oil-water UiO-66 Flux = 12.7 × 104 Size-exclusion; Hydrophilic Pore size; Roughness; Functional groups; (Zhang et al., 2018b)
L/m2·h; Rejection = interaction Hydrophilicity; Micro/nano hierarchical
100.0% structure
Oil-water PLA/ZIF-8 – Hydrophilic interaction Oil wetting ability; Diameter; Roughness; (Xiu et al., 2016)
Adsorption effect
2
Oil-water TMU-5/PES Flux = 182.0 kg/m ·h; – Hydrophilicity; Surface roughness; Pore size; (Gholami et al., 2018)
Rejection>98.0% Surface charge; Porosity
Oil-water UiO-66-NH2(1) Permeability = 2330.0 Hydrophilic interaction; Hydrophilicity; Surface charge; Functional (Cao et al., 2018)
@PAA L/m2·h·bar; Chemical and hydrogen bond groups; Roughness; Water absorption ability
Rejection>99.9% interactions of MOF
Oil-water UiO-66-NH2(0.25) Permeability = 5192.0
L/m2·h·bar
Oil-water UiO-66-NH2(1) Permeability = 4644.0
L/m2·h·bar
Oil-water UiO-66-NH2(2) Permeability = 1623.0
L/m2·h·bar
Progesterone PTFE-ZIF-8 Rejection = 95.0% Size-exclusion; Hydrogen bond Specific area; Porosity (Ragab et al., 2016)
BPA LacPAN-MIL-101-0 Rejection = 91.0% Electrostatic interaction Size and type of MOFs (Ren et al., 2018)
BPA LacPAN-MIL-101-L Permeability = 708.0
L/m2·h·bar; Rejection =
92.0%
BPA C-MIL-125-NH2-HM Rejection = 100.0% π-π interactions Zeta potential (Crespí Sánchez et al.,
4-tBP C-MIL-125-NH2-HM Rejection = 91.4% 2019)
BPA MOF0.20 Permeability = 39.5 Dilution effect; Hydrophobic Hydrophilic nanochannels (Dai et al., 2019)
L/m2·h·bar; Rejection = interactions
79.8%
Methylparaben MOF0.20 Permeability = 39.5
47.4%
Propylparaben MOF0.20 Permeability = 39.5
45.9%
Benzylparaben MOF0.20 Permeability = 39.5
51.1%
IBP MIL-100-UF Rejection = 30.9–69.7% Size effect; Electrostatic Porosity; Molecular sizes (Kim et al., 2019)
EE2 MIL-100-UF Rejection = 39.1–47.1% interactions; Hydrophobic
IBP MIL-101-UF Rejection = 42.1–71.7% interactions
EE2 MIL-101-UF Rejection = 45.1–60.5%
NOM 1 MIL-100-UF Rejection = 74.2% Electrostatic attraction; π-π Porosity; Molecular sizes (Kim et al., 2019)
NOM 2 MIL-100-UF Rejection = 86.8% interactions
NOM 3 MIL-100-UF Rejection = 93.9%
Note: Magnetic MOF-derived carbon sponge (MCS); Bisphenol A (BPA); 4-tert-butylphenol (4-tBP); Ibuprofen (IBP); 17α-ethinyl estradiol (EE2); Natural organic matter (NOM): NOM 1–
3 (humic acid and tannic acid; ratios of 10:0, 5:5, and 0:10, respectively).
investigated the incorporation of MIL-101(Cr) into polyamide layer to migration of EDCs through the compound membrane (Fig. 2C(b)). Sum-
create a MOF0.20 (0.20 wt/v % MOF) thin film composite (TFC) marily, the negative relationship between adsorption and rejection of
membrane for rejecting endocrine-disrupting compounds (EDCs), EDCs by membrane makes the enhanced rejection of EDCs, which was
which included methylparaben, propylparaben, benzylparaben, and mainly caused by the dilution effect.
bisphenol A (BPA). In comparison with the rejection of NF membrane MOF membranes exhibited excellent removal efficiency for micro-
for methylparaben (27.7%), propylparaben (25.2%), benzylparaben pollutants and the main mechanisms were hydrophobic, hydrogen
(31.3%), and BPA (64.9%), the rejection rates against methylparaben bonding and π-π interactions. However, most of the investigations on
(47.4%), propylparaben (45.9%), benzylparaben (51.1%) and BPA the elimination of micro-pollutants by MOF membranes were done in
(79.8%) by MOF0.20 membrane were significantly improved. The rea- laboratory scale. The potentiality of these researches should not be di-
son was that the incorporation of hydrophilic MOFs would generate minished. However, for commercial and practical application, MOF
water/EDCs selective channels and thus increasing the rejection of membranes must be used effectually in the actual wastewater. There-
EDCs. Fig. 2C presented the elimination mechanisms between EDCs fore, extended investigations are required to design and prepare MOF
and MIL-101-TFN membranes. As demonstrated in Fig. 2C(a), the trans- membranes that will be applied successfully in the sewage disposal
port of EDCs through dense membrane was mainly controlled by ad- plants to cleanse micro-pollutants.
sorption and diffusion. According to the contribution of MIL-101 to
elimination of EDCs, we could conclude that MIL-101-TFN membranes 2.2. Organic dye waste decontamination
showed a reduced sorption rate for EDCs with an increasing MIL-101
content, which was consistent with its hydrophilic nature (Fig. 2C(c)) Dye wastewater, as the main pollution source of textile, paint, rub-
and the generation of more hydrophilic polyamide. Accordingly, the al- ber, leather, plastic and paper industries, poses a severe threat to the
teration of hydrophilicity in polyamide layers caused by the introduc- health of human being due to its high toxicity and carcinogenic effects
tion of MOFs could decrease the adsorption and mitigated the further (Liu et al., 2021d). MOF containing membranes can be constructed
5
Table 2
Organic dye waste decontamination on MOF containing membranes.
MB ZIF-300 Permeability˃25.0 L/m2·h·bar; Rejection Size-exclusion Pore size; Stability (Yuan et al., 2018a)
= 99.6%
MB ZIF-8/PEI Permeability = 33.0 L/m2·h·bar; Electrostatic interaction Selectivity; Stability; Thickness (Yang et al., 2017b)
Rejection = 99.6%
MB UiO-66-(COOH) Permeability = 14.7–12.5 L/m2·h·bar; Electrostatic interaction Surface charge; Stability; Nanochannels (Zhang et al., 2018a)
2/prGO Rejection = 95.1% structure
MB UiO-66-rGO-1 Rejection = 98.7% Size-exclusion; Inter-layer spacing; (Guan et al., 2017)
Electrostatic interaction Numbers of nanofluidic channels
MO Cu(tpa)@GO/PES Rejection˃50.0% Specific interaction Hydrophilicity; Surface charge (Makhetha and
Moutloali, 2018)
MO CMFP/ZIF-8 Rejection = 99.0% Electrostatic interaction Functional groups; Surface charge (Park and Oh, 2017)
MO CMFP/ZIF-67 Rejection = 99.0%
MO UiO-66/PVDF Rejection = 80.0% Under investigation Specific area; Functional groups; Porosity (Denny and Cohen,
2015)
MO ZIF-300 Permeability˃25.0 L/m2·h·bar; Rejection Size-exclusion Pore size; Stability (Yuan et al., 2018a)
= 99.9%
MO ZIF-8/PEI Permeability = 51.0 L/m2·h; Rejection = Electrostatic interaction Selectivity; Stability; Thickness (Yang et al., 2017b)
81.2%
MR Zn-TCP(Fe) Permeability = 2120.0 L/m2·h·bar; Size-exclusion Nanochannels; Functional groups (Ang and Hong, 2017)
Rejection = 98.0%
MR Cu-TCP(Fe) Permeability = 1679.0 L/m2·h·bar;
Rejection = 93.0%
MR Co-TCP(Fe) Permeability = 1819.0 L/m2·h·bar;
Rejection = 94.0%
RhB UiO − 66-rGO-1 Permeability = 30.6 L/m2·h·bar; Size-exclusion; Inter-layer spacing; (Guan et al., 2017)
Rejection = 95.0% Electrostatic interaction Numbers of nanofluidic channels
RhB ZIF-300 Permeability˃25.0 L/m2·h·bar; Rejection Size-exclusion Pore size; stability (Yuan et al., 2018a)
= 99.9%
RhB JUC-160 Flux = 103.1 L/m2·h; Rejection = 99.8% Size-exclusion Pore structure; Layer spacing of MOFs (Li et al., 2019b)
RB ZIF-L/α-Al2O3 Rejection = 95.0% Size-exclusion Surface charge; Particles size (Chi et al., 2018)
RB ZIF-8/PES Permeability = 5.0 L/m2·h·bar; Rejection – – (Li et al., 2015)
= 92.5%
CR Cu(tpa)@GO/PES Rejection˃80.0% Specific interaction Hydrophilicity; Surface charge; Pore size (Makhetha and
Moutloali, 2018)
2
CR ZIF-8/PEI-HPAN Permeability = 78.0 L/m ·h·bar; Electrostatic attraction Hydrophilicity; Surface charge; Porous (Yang et al., 2017a)
Rejection = 99. 2% structure; Surface roughness
CR UiO-66-(COOH) Permeability = 13.2–10.4 L/m2·h·bar; Electrostatic interaction Surface charge; Stability; Nanochannels (Zhang et al., 2018a)
2/prGO Rejection = 97.2% structure
CR ZIF-8/PEI Permeability = 37.4 L/m2·h; Rejection = Electrostatic interaction Selectivity; Stability; Thickness (Yang et al., 2017b)
99.2%
CR JUC-160 Flux = 102.3 L/m2·h; Rejection = 99.8% Size-exclusion Pore structure; Layer spacing of MOFs (Li et al., 2019b)
R-250 JUC-160 Flux = 98.6 L/m2·h; Rejection = 99.8% Size-exclusion Pore structure; Layer spacing of MOFs (Li et al., 2019b)
AF ZIF-8/PEI-HPAN Permeability = 97.0 L/m2·h·bar; Electrostatic attraction Hydrophilicity; Surface charge; Porous (Yang et al., 2017a)
Rejection = 87.2% structure; Surface roughness
AF ZIF-8/PEI Permeability = 45.6 L/m2·h·bar; Electrostatic interaction Selectivity; Stability; Thickness (Yang et al., 2017b)
Rejection = 94.4%
TY UiO-66-rGO-1 Rejection = 98.5% Size-exclusion; Inter-layer spacing; Numbers of nanofluidic (Guan et al., 2017)
Electrostatic interaction channels
2
Ponceau MIL-53-0.5 Flux = 30.7 L/m ·h; Rejection = 99.7% Sieving effect; Electrostatic Water pressure; MOFs Loadings; Pore size (Ruan et al., 2016)
S repulsion
XO MIL-53-0.5 Flux = 33.1 L/m2·h; Rejection = 98.7%
RB5 TFN-mZIF2 Permeability = 14.9 L/m2·h·bar; Electrostatic repulsive Surface charge; Hydrophilicity; MOFs (Zhu et al., 2017a)
Rejection = 99.0% Loadings
RB2 TFN-mZIF2 Permeability = 14.9 L/m2·h·bar;
Rejection = 99.2%
Note: Rose Bengal (RB); Coomassie Brilliant Blue (R-250); Methyl Orange (MO); Eosin Y (EY); Rhodamine B (RhB); Malachite Green (MG); Methylene Blue (MB); Congo Red (CR); Methyl
Red (MR); Titan Yellow (TY); Acid Fuchsin (AF); Xylenol Orange (XO); Reactive Black 5 (RB5); Reactive Blue 2 (RB2).
through reasonable selection of MOFs type based on size exclusion to Red (CR) rejection (˃99.5%) due to the existence of several Cu-BTC
complete effective decontamination for organic dye wastewater layers. Yang et al. (2020) constructed a variety of Sm-MOF/GO nano-
(Table 2). For instance, considering that ZIF-8 particles with pore size composite membranes that were composed of GO nanosheets and sa-
between the dye (such as Rhodamine B (RhB) and Rose Red (RR)) and marium MOFs (Sm-MOFs) by vacuum filtration approach. The results
water molecules can efficiently retain organic dyes, Guo et al. (2016b) indicated that the M-0.31 (the mass ratio of the MOF material to the
and Li et al. (2015) constructed ZIF-8 separation membrane, which ex- total mass of Sm-MOF/GO nanocomposite was 0.31) owned excellent
actly achieved a high retention rate of 90.3%~97.5% and 92.5%~98.9% for permeance (26 L·m−2·h−1·bar−1) as well as high rejection (>91%) to
RhB and RR, respectively. In addition, based on the judgment that the RhB because of the enhanced interlamellar spacing attributed to the
thickness of MOF layer, the interlayer space of flaked-MOF membrane, Sm-MOF content increasing. However, the irregular nanocomposite
and the hydrophilicity/hydrophobicity of MOF particles also have a sig- membrane structure derived from the unfriendly accumulating of GO
nificant effect on removal capacity of membranes, numerous research nanosheets, which gradually decreased the dyes' rejection with an in-
efforts have been devoted. Chen et al. (2017) prepared a PVDF/Cu-BTC creasing Sm-MOF loading. Therefore, the fabricated membrane should
composite membrane on the poly(vinyl difluoride) hollow fiber sup- maintain a proper interlayer spacing, which may endow the MOF
port, which showed a water flux of 64.8 kg/m2·h and a high Congo containing membranes potential candidate for actual dye wastewater
6
Table 3
Heavy metal ions uptake on MOF containing membranes.
Pb(II) MOF-74/Nafion Adsorption = 18.0 mg/g Reduction Crystallinity; Surface area; (Albuquerque and
Size of MOFs Herman, 2017)
Pb(II) PA 300 Adsorption = 151.0 mg/g Electrostatic interactions; Competitive ion Surface charge (Efome et al., 2018b)
Pb(II) PA 808 Adsorption = 119.9 mg/g exchange; Pore filling mechanism
Pb(II) PV 808 Adsorption = 86.0 mg/g
Cu(II) MOF-74/Nafion Adsorption = 28.0 mg/g Reduction Crystallinity; Surface area; (Albuquerque and
Cu(II) ZIF-300 Permeability = 39.2 L/m2·bar; Rejection Size-exclusion Pore size; Stability (Yuan et al., 2018a)
= 99.2%
Cu(II) UiO-66-(COOH) Permeability = 21.7 ± 1.1–22.3 ± 1.4 Electrostatic interaction Surface charge; Stability; (Zhang et al., 2018a)
2/prGO L/m2·h·bar; Rejection = 83.1%–96.5% Nanochannels structure
Hg(II) PA 300 Adsorption = 265.5 mg/g Electrostatic interactions; Competitive ion Surface charge (Efome et al., 2018b)
Hg(II) PA 808 Adsorption = 254.4 mg/g exchange; Pore filling mechanism
Hg(II) PV 808 Adsorption = 213.0 mg/g
Cd(II) PAN/MOF-808 Adsorption = 225.1 mg/g – MOF loading amount; (Efome et al., 2018a)
Co-ions
Cd(II) ZIF-300 Permeability˃20.0 L/m2·bar; Rejection = Size-exclusion Pore size; Stability (Yuan et al., 2018a)
99.3%
Cd(II) UiO-66-(COOH) Permeability = 21.7 ± 1.1–22.3 ± 1.4 Electrostatic interaction Surface charge; Stability; (Zhang et al., 2018a)
2/prGO L/m2·h·bar; Rejection = 80.4–92.6% Nanochannels structure
Zn(II) MOF-74/Nafion Adsorption = 9.0 mg/g Reduction Crystallinity; Surface area; (Albuquerque and
Zn(II) PAN/MOF-808 Adsorption = 287.1 mg/g – MOF loading amount; (Efome et al., 2018a)
Co-ions
Cr(VI) ESF@ZIF-67 Rejection = 99.0% Electrostatic enhancement; Hydrophobic; Porosity; MOFs loading (Li et al., 2017b)
π-π interaction
Cr(VI) UiO-66-NH-Met/BMA Rejection = 80.0% Copolymerization Porosity; Functional (Zhang et al., 2015)
groups
Ag(I) MOF-74/Nafion Adsorption = 90.0 mg/g Reduction Crystallinity; Surface area; (Albuquerque and
As(V) ESF@ZIF-68 Rejection = 92.0% Electrostatic enhancement; Hydrophobic; Porosity; MOFs loading (Li et al., 2017b)
π − π interaction
Al(III) ZIF-300 Permeability˃20.0 L/m2·bar; Rejection = Size-exclusion Pore size; Stability (Yuan et al., 2018a)
99.5%
Co(II) ZIF-300 Permeability˃20.0 L/m2·bar; Rejection = Size-exclusion Pore size; Stability (Yuan et al., 2018a)
99.6%
Ni(II) PAA/ZIF-8/PVDF Flux =460.0 L/m2·h; Adsorption = 219.1 Electrostatic adsorption; Hydrogen Functional groups; (Li et al., 2018c)
mg/g bonding Microstructure; Roughness
treatment. Besides, Zhu et al. (2017a) constructed functionalized ZIF-8 sealed the defects via hydrogen bonding. By this method, the prepared
(mZIF) through mixing PSS and ZIF-8 in solution, and then developed hybrid membrane achieved high retention rates for MB (99.6%, 33 kg/
a TFN-mZIF membrane on polyamide layer. The hydrophilic mZIF nano- m2·h), CR (99.2%, 37.4 kg/m2·h), acid magenta (AM, 94.4%, 45.6 kg/
particles not only furnished membrane better hydrophilicity, but also m2·h) as well as MO (81.2%, 51 kg/m2·h). The excellent perm-
doubled the original permeability, while retaining the superexcellent selectivity for different dye rejection was due to the strong forces be-
retention for reactive blue 2 and reactive black 5 (up to 99.0%). Similarly, tween negative charged dyes and positive charged membrane. The
the PDA/ZIF-67@PP composite membranes through constructing biomi- lower permeation of MB caused by the thicker dye layer mainly resulted
metic poly-dopamine (PDA) and ZIF-67 layer on the polypropylene (PP) from the stronger interaction between MB (higher negative charge) and
substrate were obtained (Li et al., 2019a). Due to the introduction of hy- membrane surfaces. On the other hand, from the perspective of other
drophilic functional groups (amino and hydroxyl) on PDA material, the mechanisms, a Zr MOF growth in polyurethane foam (Zr-MOFs-PUF)
obtained PDA/ZIF-67@PP composite membrane achieved a retention membrane was constructed by Li et al. (2018a). The interception ability
rate of above 92.0% for MB and methyl orange (MO). The water flux of membranes for different charged dyes such as anionic CR, cationic
reached 216.8 kg/m2·h, which was significantly higher than pure PP MB, and neutral RB were fully explored. The result indicated that the
membrane (below 40.4%, 86.7 kg/m2·h). The size screening ensured material could simultaneously eliminate these model pollutants not
the efficient interception of contaminants molecules by separation only from CR/MB, CR/RB, and MB/RB system, but also from CR/MB/RB
membrane, while the surface functionalization of modified MOF parti- system due to the synergetic effect of Lewis acid-base interactions, hy-
cles increased their hydrophilicity and facilitated the entry of water drogen bond interactions, and electrostatic interactions (Fig. 3B). The
molecules. filtration experiments indicated that the MOF containing membrane
In addition to size exclusion, the Lewis acid-base interactions, hydro- showed excellent removal capacity of ~95.73% (CR), ~97.67% (MB),
gen bond interactions, and electrostatic interactions also became the and ~97.95% (RB). All the above investigations confirmed that the
main mechanisms in removing organic dyes. From the perspective of MOF containing membranes may be excellent material in water pro-
electrostatic interaction, the affinity of MOF containing membranes cessing for its super-efficient removal of contaminates.
with different dye molecules can be improved by regulating the charge Numerous studies proved that MOF containing membranes
characteristics of MOFs (Guo and Peng, 2018). Yang et al. (2017b) con- presented better elimination capacity than the single substrate and ma-
structed a thin and uniform ZIF-8/PEI compound membrane through in- terials. Most of the dyes were eliminated through electrostatic interac-
terfacial reaction and self-assembly approach. As indicated in Fig. 3A, tion onto the MOF containing membranes. Aside from the merits of
the PEI molecules and electropositive Zn2+ were first tightly attached using MOF containing membranes in dye elimination, practical applica-
to negative charged HPAN by electrostatic attraction, which provided tions remain a huge challenge because of its stability in wastewater and
ample binding site for ZIF-8 material generation in the PEI layer, and absence of robustness in complex pollutants present in the water
7
Table 4
Brackish water and seawater desalination on MOF containing membranes.
K+ UiO-66 Rejection = 45.7% Size-exclusion Pore sizes; Functional groups (Liu et al., 2015b)
Na+ UiO-66 Rejection = 47.0%
Ca2+ UiO-66 Rejection = 86.3%
Mg2+ UiO-66 Permeability = 0.14 L/m2·h·bar;
Rejection = 98.0%
Al3+ UiO-66 Rejection = 99.3%
Na2SO4 ZIF-8/PEI-HPAN Rejection = 3.4% Electrostatic attraction; Hydrophilicity; Surface charge; Porous (Yang et al., 2017a)
MgCl2 ZIF-8/PEI-HPAN Rejection = 8.5% Donnan effect structure; Surface roughness
MgSO4 ZIF-8/PEI-HPAN Rejection = 5.7%
NaCl ZIF-8/PEI-HPAN Rejection = 4.3%
NaCl ZIF-8 Flux =600 kg/m2·h; Rejection ˂10.0% – Membrane integrity (Duke et al., 2016)
NaCl ZIF-8 TFN Permeability = 3.4 L/m2·h·bar; Filler encapsulation Hydrophilic; Particle sizes (Duan et al., 2015)
Rejection = 98.5%
NaCl TFN-mZIF Flux =46.5 L/m2·h; Rejection = 25.3% Steric and electrostatic Hydrophilicity; MOFs loading (Zhu et al., 2017a)
repulsive effects
NaCl MOF-functionalized Flux =32.3 L/m2·h; Rejection = 99.9% – Hydrophobicity; Roughness; Pore size (Zuo and Chung, 2016)
Al2O3
NaCl ZIF-25 Permeability = 27–710 kg/m2·h·bar; Hydrogen bonding Polarity of functional group; Aperture size (Gupta et al., 2015)
Rejection = 97.0%
NaCl ZIF-71 Permeability = 27–710 kg/m2·h·bar;
Rejection = 100.0%
Rejection = 100.0%
Rejection = 100.0%
Rejection = 100.0%
+
Na UiO-66-(OH)2 Flux =0.73 kg/m2·h; Rejection = Size-exclusion Intrinsic defects; Diameter of molecules and (Wang et al., 2017)
74.9% ions; Pore size
Zn2+ UiO-66-(OH)2 Flux =0.45 kg/m2·h; Rejection =
42.5%
Fe3+ UiO-66-(OH)2 Flux =0.56 kg/m2·h; Rejection =
54.7%
NaCl UiO-66 TFN Flux =74.9 L/m2·h; Rejection = 98.8% Size-exclusion MOFs loading; Hydrophilicity; Surface area; (Kadhom et al., 2017)
NaCl MIL-125 TFN Flux =85.0 L/m2·h; Rejection = 98.6% Pore size
Na+ ZIF-8 Flux =13.5 kg/m2·h; Rejection = Size-exclusion Pore size; stability (Zhu et al., 2016b)
99.7%
K+ ZIF-8 Flux =13.5 kg/m2·h; Rejection =
99.8%
Ca2+ ZIF-8 Flux =13.5 kg/m2·h; Rejection =
99.6%
−
Cl ZIF-8 Flux =13.5 kg/m2·h; Rejection =
99.9%
Mg2+ ZIF-8 Flux =13.5 kg/m2·h; Rejection =
99.9%
Sr2+ ZIF-8 Flux =13.5 kg/m2·h; Rejection =
96.0%
−
Br ZIF-8 Flux =13.5 kg/m2·h; Rejection =
96.5%
SO2−
4 ZIF-8 Flux =13.5 kg/m2·h; Rejection =
99.5%
environment. In addition, very limited study was found regarding influ- polymeric (polyurethane (PU) and polyacrylonitrile (PAN)) with UiO-
ences of coexisting ions and operating mode on dye elimination from 66 series. The as-fabricated MOF membranes maintained equivalent
wastewater. Therefore, intensive study the factors influencing dye re- palladium (Pd) and platinum (Pt) uptake rates to the pristine MOFs,
moval and reaction mechanisms are crucial to strengthen the continual and showed good recycle performance and selectivity even in strong
use of MOF containing membranes in the decontamination of dyes. acidic solutions. Owing to the superior thermal and chemical stability
of ZIF, Yuan et al. (2018a) developed an pure ZIF-300 membrane on
2.3. Heavy metal ions uptake Al2O3 material via secondary growth method. As desired, the formed
ZIF-300 membrane showed a good size discrimination property and
To our knowledge, the heavy metal ions (such as copper (Cu), silver water stability as well as high rejection rate of 99.21% for Cu(II) and
(Ag), mercury (Hg), chromium (Cr), cadmium (Cd), nickel (Ni), cobalt water permeance of 39.2 L/m2·h·bar. Interestingly, Li et al. (2018c) fab-
(Co), lead (Pb), etc.), derived from the chemical production, mining, ricated a novel PAA/ZIF-8/PVDF hybrid membrane, and the membrane
coal, chemical fertilizer use, solid waste landfill and sewage discharge, exhibited excellent Ni(II) elimination capacity (up to 219.09 mg/g)
will circulate in the food chain and accumulate in organisms, then fi- even in hypersaline water system. As revealed in Fig. 4B, the adsorption
nally cause serious harm to humans and ecological environments mechanisms were the special hydrogen bonding interaction between Ni
(Liang et al., 2021; Liu et al., 2021c). MOF containing membranes with (II) and hydroxyl groups in ZIF-8 nanomaterial as well as the electro-
ample reactive functional groups, efficient metal ions rejection, and out- static interaction by carboxyl in PAA. Similarly, Albuquerque and
standing selectivity performances, therefore, are striking preferred Herman (2017) fabricated a MOF-Nafion matrix-based membranes by
(Table 3). As shown in Fig. 4A, Liu et al. (2019) fabricated a range of coating Nafion on the MOF-74(Ni) particles repeatedly through in-situ
fibrous MOFs membranes (FMs) through incorporating different chemically modulated microwave-assisted technique, which promoted
8
Fig. 2. (A) Schematic illustration of the structure of wrinkled ZIF-8@rGO@Sponge and its application in oil-water separation (Gu et al., 2019); (B) oil/water separation of PLA/ZIF-8
membranes (Xiu et al., 2016); (C) schematic diagram of the enhanced rejection mechanisms of EDCs by MIL-101(Cr)-TFN membranes: EDC rejection by control membrane (a); EDC
rejection by the modified membrane (b, c) (Dai et al., 2019).
metal ions removal due to the hydroxyl coordination and the chelation from the filtration experiment indicated that increasing the membrane
of sulfonic group. Specifically, the deprotonation of hydroxyl in alkaline layer obviously improved (26%) the treatable feed volume after
medium increased the adsorption capacity for metal ions. Compared doubling the membrane thickness. With the good adsorption capacities,
with Cu(II) (~29%), Zn(II) (~8%) and Pb(II) (~18%), the significant re- excellent filtration performance, re-usability and outstanding water sta-
moval capacity of MOF-74/Nafion on Ag(I) (~87%) was mainly attrib- bility, PA 808 membrane could be used as potential candidate for heavy
uted to the highest reduction potential of silver, which could be easily metal ions treatment.
to form silver clusters via in-situ reduction with ethanol. MOF containing membranes revealed fast equilibrium time, excel-
Except the stability and functional group inherent in MOFs materials, lent removal capacity, and high selectivity for targeted heavy metal
for MOF separation membranes, other parameters especially the hydro- ions, can still retain superior property even under extreme environmen-
philicity of polymer, the size of MOFs, and the thickness of membrane, tal conditions. To the best of our knowledge, the reaction mechanisms
can also significantly affects their intercept capacity for metal ions. were mainly ascribed to electrostatic interaction as well as pore filling
Efome et al. (2018b) obtained four kinds of MOFs/polymer nanofiber action. However, most of the current studies are concentrated on the se-
composite membranes (NMOM) by enmeshing mixing MOF 808 (Zr lective elimination of one target ion, and the actual water environment
(IV) based MOFs) and F300 (Fe(III) based MOFs) in PAN and PVDF via is complex and changeable. Therefore, more in-depth investigations on
electrospinning, then applied to remove Hg(II) and Pb(II) from aqueous the simultaneous dispose of multiple contaminants by MOF containing
solution. Since PAN was more hydrophilic than PVDF, NMOM (PA) pre- membranes is meaningful for the practical wastewater purification.
pared with PAN had better adsorption performance for Pb(II) and Hg(II)
than NMOM (PV) prepared with PVDF. In addition, the smaller size of 2.4. Brackish water and seawater desalination
MOF 808 made it easier to be wrapped in nanofibers than F300, leading
to better elimination performance to Pb(II) and Hg(II), but the removal Desalination is the technique of splitting salts from brackish water
performance of PA 808 composite membrane (from MOF-808) was not and seawater to generate drinking water or high purity water for indus-
as good as that of PA 300 (from F300). As already mentioned, the PA 808 trial application, which is regarded as one of the major solutions for
membrane was developed again and then possessed sorption capacity water resources scarcity. Consequently, the reasonable selection of
of 225 and 287 mg/g for Cd(II) and Zn(II), along with filtration perfor- membrane materials to achieve an excellent separation efficiency of
mance of 348 L·m2·h−1 for Cd(II) (Efome et al., 2018a). Furthermore, salt-water is necessary. Recently, the special properties of MOFs, such
Efome et al. (2019) studied the impact of membrane thickness on the as outstanding water permeability and rejection capability, have
removal efficiency of Pb(II) by PA 808 composite membrane. Results resulted in the theoretical studies and extensive experiments were
9
Fig. 3. (A) The ZIF-8/PEI (polyethyleneimine) hybrid membrane preparation process (Yang et al., 2017b); (B) illustration of the mainly potential mechanisms of dyes removal by Zr-MOFs-
PUF membrane in RB/MB/CR ternary system (Li et al., 2018a).
successively investigated toward the application of MOF containing purification, which revealed the dense and defect-free ZIF-8 membrane
membranes for preferable brackish water and seawater desalination could be used for desalination attributed to their sieving effect that
(Table 4). In 2011, Hu et al. (2011b) firstly reported the molecular sim- prevented Na+ and Cl− ions from passing through membrane. As
ulation to investigate the capability of ZIF-8 membrane for water presented in Fig. 5A, Gupta et al. (2015) simulated the seawater
Fig. 4. (A) Schematic illustration showing a) MOF fibrous membranes; b) MOFs incorporated into a single fiber; c) π-π interaction between the MOF framework and the PU polymer chain;
d) chemical structure of PU and PAN; e) Pd and Pt recovery in the hydrometallurgy process (Liu et al., 2019). (B) The adsorption removal mechanisms of Ni(II) onto the PAA/ZIF-8/PVDF
hybrid membrane in different salinity wastewaters (Li et al., 2018c).
10
11
desalination by a series of ZIF membranes with different pore sizes and hydrophilic/hydrophobic, porosity, surface roughness, thickness, de-
polarities, which further revealed that the polarity of functional groups fects of MOFs layer, and functional polarity significantly impacted on
also comprehensively affected the desalination performance of MOF their separation effects. More importantly, the excellent separation per-
containing membranes. Due to limitations of simulation study, the suc- formance in the fields of oily and micro-pollutant removal, organic dye
cessful preparation of the water stable MOFs membranes would also waste decontamination, heavy metal ions uptake, and brackish water
verify the feasibility for desalination process by experiments. Wang and seawater desalination endows MOF containing membranes great
et al. (2017) manufactured a continuous and high-quality UiO-66- application prospects.
(OH)2 membrane using post-synthetic defect healing method, which
exhibited the alleviation of ligand-lacking disadvantages in membranes. 3. Environmental application assessment of MOF containing
As depicted in Fig. 5B, the membrane selectivity was mainly dominated membranes
by the diameter of probe molecules or ions. Moreover, the experimental
results proved that the UiO-66-(OH)2 membranes exhibited different With the rapid development and extensive research of MOF contain-
salt ions rejection rate (e.g., 26% for Na+, 42.5% for Zn2+, and 54.7% for ing membranes, it is necessary and significant to investigate the envi-
Fe3+) on the basis of size exclusion mechanism. While the relatively ronmental application potential of MOF containing membranes. It's
low water flux (e.g., 0.73 kg/m2·h for Na+, 0.45 kg/m2·h for Zn2+, important to note that the environmental application of membranes is
and 0.56 kg/m2·h for Fe3+) could be owing to the delayed shifts of affected by the quality of the membranes. For MOF containing mem-
water by the slow spread of the hydrated ions, which mainly related branes, its quality is mainly affected by stability performance, antifoul-
with the single-file diffusion in microporous channels. Although the ing characteristics, compatibility, and dispersity. Accordingly, it is
above research suggested the great potential of UiO-66 separation beneficial for us to understand the specific effects of above factors on
membrane for water desalination, the difficulty in constructing dense, the membrane quality, and their corresponding solutions.
defect-free MOFs membranes made the desalination effect obtained in
the experiment was still somewhat different from the theoretically cal- 3.1. Stability performance
culated results. Therefore, more research efforts should be devoted to
the preparation of well-inter-grown, continuous, and dense membrane Owing to the instability of ligand-metal bonds, the majority of earlier
for improving the water flux and salt retention performance. discovered MOFs are susceptive to the humid environment, resulting
In addition to the above factors, the MOF adding resulted in modifi- the instability of MOF separation membranes in water. The water stabil-
cation of the membranes in the aspect of hydrophilicity, surface charge, ity, which includes thermodynamic stability (depends on the free en-
and overall porosity also affect the desalination performance of mem- ergy of hydrolysis reaction of MOFs) and kinetic stability (determined
branes. For instance, Kadhom et al. (2017) embedded MIL-125 and by the activation energy barrier). Water stability is mainly influenced
UiO-66 into the TFN membrane and further tested the effects of differ- by the interaction between water molecules and framework structure.
ent MOFs as additives in membranes' performance. The results found Specifically, the factors that affect the stability of MOFs can be catego-
that by adding 0.15 wt% of UiO-66, the water flux increased from 62.5 rized into two major types: (I) Effects of metal-ligand coordination
to 74.9 L/m2·h, while the water flux reached to 85.0 L/m2·h by adding bond. MOFs, built from organic ligands and metal ions (clusters) con-
0.3% of MIL-125, which was mainly attributed to hydrophilic nature nected by coordination bonds, have evolved as a significant class of po-
and the water transportation channels of MOFs. Owning to the surface rous nanomaterials. Accordingly, the properties of metal cations such as
charge and pore size of MOFs, the water flux-salt rejection trade-off ba- valence (positive correlation), and radius (negative correlation), along
sically remained same in both cases (≥98.5%). Zirehpour et al. (2016) with the ligand dissociation constant (pKa) have a certain influence on
successfully incorporated the hydrophilic MOF nanomaterial (Cu-BTC) the coordination bond strength, which further determines their ther-
into cellulose acetate/triacetate (CTA) material for water desalination. modynamic stability (Lu et al., 2014; Yuan et al., 2018b; Zhang et al.,
In comparison to the unmodified membranes, the water flux was signif- 2019b). Specially, to compensate for the high charge densities carried
icantly improved from 10.0 to 30.0 L/m2·h by adding 3.0 wt% of Cu-BTC, by high-valence metal ions, metal ions (clusters) need to be connected
which was consistent with the selective water absorption capacity and with excess of coordination ligands or carboxylate based linkers to form
the water transportation channels provided by highly porous structure a high-coordination number structure thus facilitating the water stabil-
and hydrophilic surface of Cu-BTC materials. Correspondingly, due to ity of MOFs (Yuan et al., 2018b). Zhou's research group prepared a series
the improved hydrophilicity, Jee et al. (2015) demonstrated the water of PCN-MOFs by combining Zr(IV) with different organic ligands (Feng
flux of acidified Cu3(BTC)2 added PVDF membranes was 558 L/m2·h, et al., 2013; Jiang et al., 2013). As shown in Fig. 6A, Zr(IV) and the por-
which was 72.3% higher than that of the pure PVDF membrane. phyrin ring constructed PCN-222 with eight ligands and PCN-224 with
To our knowledge, the selection of MOF materials applied for desali- six ligands through different coordination structures. However, the as-
nation process was highly rely on its water stability, pore size as well as sembly of Zr(IV) with ten ligands that could lead to more stable PCN-
pore aperture. A large number of investigations have revealed that UiO- 225 (Fig. 6B), which had both high thermal stability (≥ 350 °C) and
66 and ZIF-8 materials were effective in separating univalent ions and strong chemical stability. Additionally, the ligand pKa is also applied to
suitable for treating high concentration brine (Abdullah et al., 2021). determine the coordination strength of metal-ligand bond. And the
In addition, the specific removal mechanism for desalination process pKa sequence of common organic ligands as following: soft bases
was size-exclusion. However, applications of MOF containing mem- nitrogen-containing heterocyclic ligands (pyrazoles > imidazoles) >
branes for wastewater purification especially in brackish water and sea- hard bases carboxylic acid ligands (dicarboxylates > carboxylates).
water desalination are still in its infancy. Future research on MOF Due to the high pKa values of nitrogen-containing heterocyclic ligands,
containing membranes in desalination process will concentrate on the a class of stable MOFs through coordinating with low-valence metal cat-
modification of either membrane surface or MOFs to prepare the differ- ions for example Co(II), Zn(II), Cu(II) and Ni(II) were obtained (Desai
ent materials with excellent selectivity and permeability. et al., 2016; Kirchon et al., 2018; Li et al., 2016; Zhang et al., 2019a). No-
To summarize, we briefly introduced the application of MOF tably, the above research results were consistent with the “hard-soft,
containing membranes for water treatment, and found that MOF acid-base” theory. Stable MOFs can be assembled via hard bases (car-
containing membranes owned unique structure and excellent separa- boxylate-based ligands) and hard acids (high-valence metal ions for in-
tion properties. In addition, the effective separation of pollutants by stance Al(III), Cr(III), Fe(III), Ti(IV) and Zr(IV)), or obtained through soft
MOF containing membranes were mainly based on size-exclusion, bases (nitrogen-donor ligands) and soft acids (low-valence metal ions
electrostatic interaction, hydrogen bonding, π-π stacking interactions such as Co(II), Zn(II), Cu(II) and Ni(II)). (II) Impacts of framework
and so on. For the specific contaminants, the surface charge, steric-hindrance. In addition to the strong coordination bonds, the
12
Fig. 5. (A) Simulation system for water desalination through a ZIF membrane. An aqueous NaCl solution with 0.5 M NaCl and pure water bath are on the left and right chambers of the
membrane, respectively (Gupta et al., 2015). (B) Separation performance of polycrystalline UiO-66-(OH)2 membrane for the removal of metal ions and methyl blue (MB) in aqueous
solutions (a) and illustration of single-file diffusion of water molecule and hydrated Mn+ ion (b) (Wang et al., 2017).
existence of framework steric-hindrance can also improve the kinetic doping metal ions, modifying organic ligands, and selecting ligands
stability of MOFs. Framework steric-hindrance survive the attack of with special structures. Wang et al. (2015a) fabricated ultra-stable
guest molecules, and thus provide activation energy barrier. Impres- MOFs (Zr-DTDC) containing thiophene-type ligand, in which the intrin-
sively, the multi-coordination structure derived from the coordination sic hydrophobicity and steric hindrance effect derived from methyl
between high-valence metal ions and organic ligands will produce the groups can prevent the attack of framework from guest molecules. Fi-
steric resistance effect, which made the lattice maintain good stability. nally, Zr-DTDC maintained excellent stability even immersing in
Recently, researchers found that steric-hindrance effect can be consid- water, boiling water, HCl solutions, and NaOH solutions for 1 or 7 days
erably enhanced through introducing hydrophobic groups/ligands, (Fig. 6C). Nguyen and Cohen (2010) developed amide-functionalized
13
Fig. 6. (A) Coordination strategy of metal clusters and organic linkers in porphyrin zirconium MOFs (Feng et al., 2013); (B) Zr6(μ3-O)4(μ3-OH)4(OH)4(H2O)4(COO)8 cluster (above) and
view of the structure of PCN-225 along the b-axis with two types of channels (below). The Zr, O, C, N atoms are shown in pink, red, gray and blue, respectively. H atoms are omitted
for clarity (Jiang et al., 2013); (C) PXRD patterns (a, c) and N2 adsorption-desorption isotherms (b, d) for Zr-DTDC treated with different methods (Wang et al., 2015a).
MOFs through the introduction of hydrophobic alkyl chains via variations of organic linkers could exclude the water molecules ap-
postsynthetic modification, which formed a barrier between water proaching the central metal ions and then attacking the framework
molecules and metal ion structures in the pore cavity of MOFs and structure. Besides, Liu et al. (2015a) fabricated a series of PCN-MOFs
endowed MOFs super-hydrophobicity as well as excellent water stabil- with enhanced pore apertures using extended porphyrinic linkers. The
ity. Zhu et al. (2016a) enhanced the hydrophobicity of MOFs by doping unique ftw-a topology, bulky porphyrin ring and Zr6 cluster with high
metal ions, which provided a new discovery for exploiting exceptionally connectivity could lock the unstable structure and further yielded
water stable heterometallic MOFs compared with parent STU-1. frameworks with enhanced stability.
Bellarosa et al. (2013) found that the hydrophobic treatment of organic As a conclusion, the bond strength of metal-ligand determines the
ligands could be realized by connecting halogens (such as fluorine, bro- thermodynamic stability of MOFs. However, the main structural charac-
mine, etc.) to organic ligands. The results showed that hydrophobic teristics of its kinetic stability are attributed to steric hindrance effect.
14
Obviously, MOFs with strong metal-ligand coordination bond and sig- performance were synthesized by incorporating MOF particles into or-
nificant framework steric-hindrance tend to be more stable. Based on ganic polymer membrane materials to improve their antifouling prop-
the above discussions, in addition to selectively synthesizing stable erties (Gholami et al., 2018; Ma et al., 2017; Sun et al., 2017). Zhu
MOFs on the strength of “hard-soft, acid-base” theory, there are the fol- et al. (2017a) modified ZIF-8 by PSS with hydrophilic groups and suc-
lowing six common methods to enhance the chemical stability of MOFs: cessfully prepared a PAN hybrid membrane material for nanofiltration.
(i) ligands containing one or more hydrophobic groups are introduced The results revealed that ZIF-8 modified by PSS could not only effec-
into frameworks (Wu et al., 2010); (ii) the enhancement of the hydro- tively improved the hydrophilicity of hybrid membrane surface, but
phobicity in MOFs channels by doping metal ions (Zhu et al., 2016a); also further increased the nanofiltration performance of hybrid mem-
(iii) stability maintained through the shielding effect of functional brane material. Although studies have shown that hydrophilic modifica-
groups (nonpolar alkyl) on the central metal ions (Taylor et al., 2012); tion can enhance the antifouling properties of MOF membranes, the
(iv) fluorinated pore surfaces to obtain fluorinated MOFs (FMOFs) surface roughness of hydrophilic film is easy to be destroyed, which
(Yang et al., 2011); (v) hydrophobic treatment of ligands through leads to the decrease of MOF film stability. Therefore, the exploitation
reacting with halogens (such as fluorine, bromine, etc.) (Bellarosa of MOF membranes with excellent stability and high antifouling prop-
et al., 2013); and (vi) the stability are changed by integrating the me- erty is the key. Furthermore, for MOF membranes that have been pol-
dium and long alkyl groups within MOFs (Nguyen and Cohen, 2010). luted, exploiting gentle cleaning agents as well as increasing the
recyclability of MOF membranes are not only an effective method to
3.2. Antifouling characteristics lower development costs, but also reduce the environmental pollution
of disused membrane materials.
The degradation of water productivity, the deterioration of permeate
quality and the shortening of lifespan caused by fouling make mem- 3.2.2. Low surface roughness
brane fouling the main obstacle for the wider application of MOF con- The surface roughness is a significant parameter that can affect
taining membranes, which usually causes higher membrane membrane fouling performance by improving the speed of adhesion
replacement and operating cost (Mo et al., 2012). Hence, the design of to the membrane surface. It is normally regarded that smoother surface
antifouling membrane is not only the vital to solve membrane fouling membranes are more prone to antifouling. However, contradictory re-
problems, but also is one of the most important factors promoting the sults are also reported due to the increasing agitation degree of the
practical application of membranes. Obviously, the properties of mem- membrane surface with the roughness enhancing, which hinders the
brane (hydrophobicity/hydrophilicity, surface roughness, and surface adsorption of pollutants onto membrane surface. Therefore, the
charge) strongly influence the membrane fouling. Accordingly, in the influence of membrane surface roughness on all membrane property
following content, we will explore the prevention and control of mem- is debatable. It is generally believed that smoother surface exhibits
brane pollution from the perspective of membrane design (i.e. the con- weak elimination for organic pollutants due to smaller surface area. In
trol of membrane surface properties). summary, investigations are currently concentrated on the diminution
of membrane surface roughness. It is universally known that MOFs
3.2.1. High surface hydrophilicity usually owns a smooth surface, and its inherent low surface roughness
Due to the existence of hydrogen bond interaction between the contributes the superior antifouling properties to MOFs membranes.
water molecules and hydrophilic membrane surface, a compact and or- Mohammadnezhad et al. (2018) found that PES membrane modified
derly hydration layer is formed on the membrane surface. The hydration with Ce-MOF nanoparticles showed ameliorated antifouling feature,
layer limits the fundamental interaction between contaminants and and also had a slightly diminished sensibility to PES membranes. They
membranes and thus endows MOF containing membranes the charac- found that these merits existed owing to the smoother surface rough-
teristic of antifouling (Zinadini et al., 2014). However, the absences of ness of Ce-MOF/PES mixed matrix membrane. Park et al. (2017) directly
hydrogen bonds between the hydrophobic surface and water molecules elucidated a powerful correlation between the fouling resistance and
make MOFs membrane prone to be polluted by hydrophobic sub- the RO membrane surface roughness by fabricating an RO membrane
stances. Moreover, the hydrophobicity of the membrane shortens mem- with a thin active layer and weak surface roughness on a porous and hy-
brane lifetime, enhances required energy, and reduces water flux. In drophilic MOF/PSF layer. The porosity and hydrophilicity of the MOF/
consequence, for the sake of preventing membrane pollution and reduc- PSF support layer resulted in the formation of the TFC RO membrane
ing operation cost, developing membranes with antifouling properties with low surface roughness, which finally increased the fouling
through hydrophilic modification is of great significance to the prepon- resistance and water flux. Due to remarkable progress of macroscale
derances of MOFs separation membrane. The hydrophilicity/hydropho- super-lubricity of nanomaterials, a number of 1D and 2D materials,
bicity of MOFs is primarily dominated by the open metal sites and the including GO, carbon nanotubes (CNTs), and transition metal
ligands. For instance, Liu et al. (2017) fabricated hydrophilic UiO-66 dichalcogenides (TMDs) have been proved great potential in changing
polycrystalline membranes through involving abundant hydroxyl func- the antifouling characteristic of membrane by reducing the surface
tional groups in its structure to endow UiO-66 membrane hydrophilic roughness (Gong et al., 2017; Koren and Duerig, 2016; Zhai and Zhou,
binding sites, which provided an remarkable antifouling property for 2019; Zhang et al., 2013). As exhibited in Fig. 7B, Yang et al. (2019) eval-
separation membrane. Recently, carbon-based fillers for instance GO, uated the antifouling performance of CA, CA/GO and CA/MOF@GO ultra-
as hydrophilic additives for the functionalization of MOF membranes filtration membrane through flux recovery ratio (FRR), which could
have obtained keen interest of researchers such as Firouzjaei et al. positively feedback the antifouling performance of membranes. The
(2018), which confirmed that the hydrophilicity of membranes could higher FRR value of CA/MOF@GO membrane (88.13%), compared with
be enhanced by GO. As shown in Fig. 7A, with the introduction of GO, CA membrane (49.78%) and CA/GO membrane (61.17%), was in confor-
the contribution of contact angle on the antifouling and anti- mity with the surface roughness observed from AFM images. AFM anal-
biofouling performances of GO TFN and GO-Ag-MOF TFN membrane ysis indicated that the blended membranes had smoother surfaces
gradually increased compare with TFC and Ag-MOF TFN membrane, compared with CA and CA/GO membrane, which prevented sedimenta-
respectively. To be noted that, their superior hydrophilicity imparted tion of protein in the valleys and improved the elimination capacity.
by abundant oxygen-containing functional groups (for example, epox- Wang et al. (2016a) reported that ZIF-8@GO composite membranes
ide, hydroxyl, carboxyl and carbonyl) that in turn contributed to the showed excellent water purification performance with enhanced anti-
increasement in membrane fouling mitigation and permeation flux microbial activity. However, the research of MOFs membrane supported
(Makhetha and Moutloali, 2018). In addition, a variety of MOF by CNTs and TMDs had not been found, which would have great poten-
inorganic-organic hybrid membranes with excellent hydrophilic tial in the future.
15
Fig. 7. (A) Parameters contribute to anti-biofouling and antifouling properties of different membranes (Firouzjaei et al., 2018); (B) Water flux recovery ratio of the fabricated membranes
(Yang et al., 2019); (C) The fluorescent images of E. coli bacteria on the membrane surface of (a) nascent TFC and (b) in-situ Ag-MOFs TFC functionalized membranes, stained with SYTO 9
(green) and PI (red) for live and dead bacteria, respectively (Seyedpour et al., 2019).
3.2.3. Negative surface charge the charge properties of membranes. Lin et al. (2019) also found that
Apart from the surface hydrophilicity and surface roughness men- fouling resistance occurred in mHKUST-1@PA membrane with the
tioned above, surface charge will also affect the fouling resistance of introduction of mHKUST-1, thus resulting in MOF membranes main-
the MOFs membranes. For most charged contaminants, electrostatic in- taining a high separation and long-term performance after 30-days con-
teractions between the membrane and the component affect the level of tinuous operation. To be noted that investigations were made lately to
fouling, particularly during the initial stages of fouling. The screening of fabricate positively charged membranes because they can behave as
electrostatic repulsion between the charged membrane surface and the barriers for cations. Moreover, recent research revealed that the addi-
co-ions in aqueous solution is usually listed as a prerequisite for reduction of zwitterionic charged material could play a more efficient role
ing the fouling. In most cases, MOF separation membrane surfaces are in antifouling compared with the traditional negatively/positively
designed to be negatively charged due to most of the pollutants depos- charged membrane surface (Rana and Matsuura, 2010). Although the
ited on the surface are negative electric charge. For example, Seyedpour above research was not confirmed in MOF membranes, these charged
et al. (2019) fabricated functionalized membrane through the fastening membranes will show great potential in membrane fouling resistance
of Ag-MOFs on TFC membrane surface and subsequently investigated with the development of the preparation of MOF membranes.
their antibacterial properties. As depicted in Fig. 7C, large amounts of
P. aeruginosa strains lived on TFC membrane surface, while the viable 3.3. Other properties
bacteria measured on Ag-MOFs membrane surface reduced dramati-
cally. The obtained membranes showed low fouling and high solute re- 3.3.1. Compatibility between MOF fillers and polymer matrix
jection tendency, owing to the dissociated negative charge from It is well acknowledged that the unique properties of MOF nanopar-
unreacted and free-contact carboxyl groups in Ag-MOFs dominated ticles make the compatibility between polymer and MOFs is much
16
better than other traditional inorganic materials. However, in consider- MMMs with ZIF-8 nanomaterials coated by an ultrathin PDA layer. It is
ation of insufficient compatibility derived from the inevitable interfacial conducive to enhance the compatibility because of the hydrogen bond
defects, the main advantage of MOFs will be difficult to fully integrated interaction between tertiary amine in Tröger's Base (TB) based
with the advantages of polymers. Moreover, problems such as MOF polymers and plentiful secondary or primary amine groups on PDA mol-
nanoparticle aggregation, poor dispersion, and non-selective interfacial ecules. Inspired by the design route, MOF containing membranes con-
voids frequently occur, leading to non-improved membrane quality, sist of hydrophilic polymer poly(vinyl alcohol) (PVA) and SO3H-MIL-
which may reduce the selectivity and stability (Zhu et al., 2017a). Con- 101-Cr@PD coating were fabricated and used for separation of ethylene
sequently, the compatibility between MOFs and polymers also urgently glycol (EG) (Zhang et al., 2017). By observing the optimal loading capac-
requires a conclusive discussion. Surface modification strategies have ity of the SO3H-MIL-101-Cr-PVA membrane (20 wt%) and SO3H-MIL-
been used as an efficient strategy to improve the compatibility between 101-Cr@PD-PVA MMMs (30 wt%) in Fig. 8A, PD layer could improve
polymers and MOF nanoparticles: (1) Polymer layer-coated MOFs. Ear- the selectively, permeability, and EG separation performance of mem-
lier researches have verified the compatibility with polymer matrix branes. This mainly because of the enhanced compatibility between
could be enlarged by coating polymer layer on the MOF fillers surface. PVA and MOF, which was attributed to the hydrogen bond interaction
Polydopamine (PDA), the most typical representative, have been exten- between the hydroxyl in PVA and the plentiful amine groups in PD;
sively studied. Wang et al. (2016c) constructed ZIF-8-polyimide (PI) (2) Polymer and functional groups-grafted MOFs. Sun et al. (2017)
Fig. 8. (A) Effects of (a, b) SO3H-MIL-101-Cr@PD, (c, d) SO3H-MIL-101-Cr different loadings in membrane on PV performance of EG aqueous solution (water content: 20 wt%) at 343 K
(Zhang et al., 2017); (B) fluxes (a) and rejections (b) of the PA, PA/ZIF-8 (O), and PA/ZIF-8 (LBL-#4) membranes (Wang et al., 2015b).
17
synthesized poly(sulfobetaine methacrylate) (PSBMA)-modified MOF in both flux and rejection were also achieved compared with PA/ZIF-8
(UiO-66-PSBMA) and then incorporated it into PSf casting solution. membrane (Fig. 8B). Yu et al. (2017) also presented a facile approach
The hydrophilic PSBMA brushes grafted on UiO-66-NH2 could for synthesizing AAO/MIL-53-NH2 membranes by in-situ generation of
effectively promote the dissolution of UiO-66-PSBMA in the PSf solu- MOF plates in the channels of anodized aluminum oxide (AAO) mem-
tion, and the hydrophobic interactions between the hydrophobic chains branes, which could efficiently restrain the aggregation of MOFs in poly-
in PSf and PSBMA contributed to a better compatibility of MOF nano- mer. Additionally, the commonly used in situ self-assembly (Zhang
crystal with polymer. Additionally, the polyethylenimine (PEI) (Xin et al., 2014) and spray self-assembly (Fan et al., 2013) methods have
et al., 2015) and phenyl acetyl group (Venna et al., 2015) was also also been adopted for effectively enhancing dispersity of MOF particles.
grafted on MOFs to improve the compatibility of filler-polymer. From the summary shown in Fig. 9, we can conclude that the follow-
(3) Ionic liquid (IL)-decorated MOFs. To our knowledge, it is surely a ing three types of MOFs with a good water stability: (a) Carboxylate MOFs
challenge for micro-sized MOFs to attain strong affinity and defect- deriving from high-valence metal ions; (b) MOF containing heteroatoms
free binding with polymer. To address this problem, Lin et al. (2016) such as nitrogen, phosphorus or sulfur; (c) MOFs blocked with metal ions
immobilized the thin IL named 1-ethyl-3-methylimidazolium bis or modified by hydrophobic pore surfaces. Compared with those instabil-
(trifluoromethylsulfonyl)imide (Emim[Tf2N]) layer on the micron- ity MOFs, the above mentioned frameworks usually have stronger
scale HKUST-1 to remove interfacial voids in membranes. In contrast coordination bond and steric resistance, which can ensure stronger stabil-
to the membranes with only HKUST-1 incorporation, the favorable IL/ ity. Although relevant researches have shown that when MOFs mem-
polymer and MOF/IL interaction served as a filler/polymer interfacial branes are seriously polluted, the regeneration of membrane can be
binder, which could restrict the interfacial voids formation and further realized through the use of appropriate chemical cleaning agent such as
enhanced the affinity of MOF/polymer. surfactant, oxidant, acid, alkali, complexing agent, and enzyme. However,
researchers have been also committed to increase the membrane anti-
3.3.2. Dispersity of MOF nanoparticles in matrix fouling performance. And the higher surface hydrophilicity, lower surface
Generally, better dispersibility will result in better performance of roughness, and more negative surface charge can improve antifouling
membranes, which makes the good dispersibility of MOF nanoparticles characteristics of MOF containing membranes. In addition, the excellent
in the polymer as the main concern on the optimization of membrane compatibility and dispersion of MOF fillers in polymer matrices ensure
performance. Specifically, MOF agglomerates may be generated during the fabrication of uniform membrane with few defects, which plays a
the dispersion of a maximum MOF loading, which may resulted in a vital role in the formation of high-quality membranes.
reduce in rejection rate and flux enhancement, and accompanied by a
exacerbation of membrane quality after long-term running owing to 4. Conclusions and future perspectives
swelling (Li et al., 2017a). In addition, the low MOFs loading usually
results in lower specific adsorption sites and/or separation channels/ In this review, we provided an explicit summary about the latest de-
sites, which finally lead to a low selectivity (Wang et al., 2019b). In velopment of MOF containing membranes for water treatment. Specifi-
order to make the MOFs more dispersive and obtain the high MOF cally, the applications of MOF containing membranes for removing oily
concentration, it is urgent that improving the dispersion approaches of and micro-pollutants, heavy metal ions, organic dye, brackish water and
the MOF to increase its dispersibility and thereby obtaining a more uni- seawater, had also been introduced. Additionally, the stability of MOFs,
form surface MOF containing membranes. To this end, the following the antifouling performance of membranes, the compatibility between
methods are summarized according to relevant research to address polymer matrix and MOF fillers, along with the dispersity of MOF nano-
the less prominent dispersion of MOF nanoparticles in polymer phase: particles in polymer, had been analyzed carefully to better evaluate the
(1) Pre-dispersing MOF nanoparticles. It is difficult to fabricate a environmental applications of MOF containing membranes. The unique
uniform MOF containing membrane with uniformly distributed MOF physicochemical properties, excellent removal performance, and the
particles through directly disperse MOFs in a polymer solution. There- achievable potential of environmental application through rational de-
fore, Ren et al. (2019) confirmed that MIL-53(Fe) nanoparticles in the sign strategies, made MOF containing membranes potential scavengers
67-MIL-PVDF membrane, which synthesized by pre-dispersing in for water environmental remediation.
acetone, could showed better dispersity than that of without pre- Although many investigations about their actual application have
dispersion. (2) Surface functionalization of MOF nanoparticles. One of been gradually solved for the past few years, we should also realize
the most distinctive characteristics of MOFs consist in their potential that the exploration for MOF containing membranes is still at the basic
for functionalization on surfaces, which can provide ideal approach for research stage. In order to realize the practical application of MOF mem-
significantly improving the MOFs dispersion. Inspired by above point branes and construct thorough relationship between MOF containing
of view, a surface modification of CAU-1 particles using PEI-grafting membrane's structure-mechanisms-performances, the following issues
modification was introduced to fabricate MMMs for improving the still need to be focused on at the next stage:
dispersity of MOFs materials in polymer solution (Guo et al., 2018).
The results indicated that after making the 1 wt% MOF suspension liq- (1) Application explorations: investigation of the broader behavior
uids stand for 0–3 h, the CAU-1 functionalized with PEI remain stable, and efficiency applications of MOF containing membranes in
while CAU-1 suspension aggregates quickly. Additionally, results water treatment through more experimental works.
through surface functionalization of MOFs to effectively inhibit their ag- i) Synchronous separation of multiple pollutants on multi-functional
glomeration, such as surface modified with amino groups (−NH2) (Ma membranes. In terms of the complex pollutant composition in the
et al., 2016), hydroxyl groups (–OH) (Kitao et al., 2017), and long alkyl actual water environment, the first consideration should be the
chains (Guo et al., 2016a), have also been achieved successfully; (3) De- synchronous separation of multifunctional MOF containing
velopment of suitable preparation methodologies. To overcome the membranes. In consequence, it is important to further discuss
poor utility of MOF containing membranes derived from the aggrega- and study how to improve the filtration performance for multiple
tion of MOF particles, a series of suitable preparation methodologies pollutants under complicated conditions by the combination of
were investigated to improve the dispersity of MOF nanoparticles in MOFs with other nanomaterials to fabricate original versatile
polymer. For instance, Wang et al. (2015b) fabricated a fresh approach nanocomposites, which can further affect extensive applications,
called layer-by-layer (LBL) self-assembly to design a PA/ZIF-8 separa- because they have the strengths of both constituents. In addition,
tion membrane. In such a process, the pre-fabricated ZIF-8 consideration should also be made toward the exploration of the
nanomaterials were not dispersed in aqueous/organic phases, thus many influencing factors that may influence MOF containing
avoiding the aggregation of ZIF-8 particles. The improved performances membrane's separation behavior in the actual application.
18
Pre-dispersing MOF nanoparticles

Surface functionalization of MOF nanoparticles
Development of suitable preparation methodologies
Better dispersity endows the membrane

superior performance
Influencing factors
Metal-ligand coordination bond Antifouling membranes
Framework steric-hindrance
High surface hydrophilicity
Low surface roughness
Negative surface charge
Cleaning membranes
Oxidant
Complexing agent
Acid and alkali
Surfactant and enzyme
Surface modification strategies
Polymer layer-coated MOFs

Polymer and functional groups-grafted MOFs
Ionic liquid (IL)-decorated MOFs
Fig. 9. The influencing factors and corresponding countermeasures of MOF containing membranes for environmental applications.
ii) Decontamination in harsh/complicated environments. Challenges comprehensive understanding of transport mechanisms of multiple
remain for the further industrial applications of MOF containing contaminants by different MOF containing membranes are still
membranes due to the long-term instability under actual separa- needed. To reveal the mechanism of simultaneous reaction for con-
tion environment. In the next stage, more researches on the taminant removal by MOF containing membranes, the multifunc-
long-term chemical stability of membranes in harsh/complicated tional decontamination mechanism should be closely determined
environments (high temperatures, acidic/basic, and sophisticated due to the removal behaviors of contaminants on membranes are
organic solvent systems) are urgently required. Future efforts very complicated. In simultaneous systems, the total removal of pol-
should focus on investigating membranes that not only have a lutants may be attributed to the catalytic oxidation, adsorption, per-
long-term chemical stability under realistic separation environ- meability, ultrafiltration, and some other mechanisms, which need
ment, but can also without alter the surface properties after sepa- to be investigated more thoroughly at the next stage.
ration applications.
Overall, this critical review offers a more comprehensive and clearer

(2) Mechanism investigations: explication of the synergy effect of
insight of water treatment by MOF containing membranes. Although
multiple mechanisms and their respective roles.
some technical bottlenecks still exist in the application of membranes,
i) Develop sophisticated characterization techniques. In addition to in view of the great application potential of MOF containing membranes
study the self-synthesis and application of MOF membranes, in environmental restoration, with more investment in thorough re-
novel analytical methods are also constantly developing and im- search, the MOF containing membranes can be used as commercial
proving to explore the mechanisms between membranes and pol- membrane in foreseeable future.
lutants. The employ in-situ characterization methods (e.g. SEM,
TEM, FTIR, XRD, and XPS) are very popular to investigate the mech- Declaration of competing interest
anism of material synthesis, which could receive controllable or
perfect MOF containing membranes, and improve their application The authors declare that they have no known competing financial
efficiency. For extensively understanding the mechanisms of interests or personal relationships that could have appeared to influ-
membrane fouling, membrane resistance, and water treatment, ence the work reported in this paper.
further investigations should put more attentions in developing
the more sophisticated characterization techniques. Acknowledgments
ii) Determine the multifunctional decontamination mechanism. At
present, the screening mechanism of membranes for pollutants is This work was supported by National Key Research and Develop-
not yet clear, and a lot of research works focusing on the ment Program of China (2017YFA0207002), the National Natural
19
Science Foundation of China (21906052, U2067215), the Research Fund Gong, X., Huang, Z., Zhang, H., Liu, W., Ma, X., Xu, Z., Tang, C.Y., 2020. Novel high-flux pos-
itively charged composite membrane incorporating titanium-based MOFs for heavy
Program of Guangdong Provincial Key Laboratory of Radionuclides Pol- metal removal. Chem. Eng. J. 398, 125706.
lution Control and Resources (2017B030314182). Gu, J., Fan, H., Li, C., Caro, J., Meng, H., 2019. Robust superhydrophobic/superoleophilic
wrinkled microspherical MOF@rGO composites for efficient oil-water separation.
Angew. Chem. Int. Ed. 58, 5297–5301.
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Science of the Total Environment 800 (2021) 149662

Contents lists available at ScienceDirect

Science of the Total Environment

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

Recent advances in metal-organic framework membranes for water

• The developmental timeline of MOFs-

First MOF membranes

First MOF membranes

Bare MOF membrane used for desalination;

Explored the effect of MOFs The effects of the chargeability

MOF hybrid UF membrane firstly Thin-film composite membrane with

Novel high-flux positively charged

Targets Membranes Key performance Mechanisms Inﬂuence factors Ref

Targets Membranes Key performance Mechanisms Inﬂuence factors Ref

Targets Membranes Key performance Mechanisms Inﬂuence factors Ref

Targets Membranes Key performance Mechanisms Inﬂuence factors Ref

 Pre-dispersing MOF nanoparticles

Better dispersity endows the membrane

Surface modification strategies

 Polymer layer-coated MOFs

Overall, this critical review offers a more comprehensive and clearer

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Pre-dispersing MOF nanoparticles

Polymer layer-coated MOFs