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Review on Metal−Organic Framework Classification, Synthetic

Approaches, and Influencing Factors: Applications in Energy, Drug
Delivery, and Wastewater Treatment
Vadia Foziya Yusuf, Naved I. Malek, and Suresh Kumar Kailasa*

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ABSTRACT: Metal ions or clusters that have been bonded with organic linkers to create
one- or more-dimensional structures are referred to as metal−organic frameworks (MOFs).
Reticular synthesis also forms MOFs with properly designated components that can result in
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crystals with high porosities and great chemical and thermal stability. Due to the wider
surface area, huge pore size, crystalline nature, and tunability, numerous MOFs have been
shown to be potential candidates in various fields like gas storage and delivery, energy
storage, catalysis, and chemical/biosensing. This study provides a quick overview of the
current MOF synthesis techniques in order to familiarize newcomers in the chemical
sciences field with the fast-growing MOF research. Beginning with the classification and
nomenclature of MOFs, synthesis approaches of MOFs have been demonstrated. We also
emphasize the potential applications of MOFs in numerous fields such as gas storage, drug
delivery, rechargeable batteries, supercapacitors, and separation membranes. Lastly, the
future scope is discussed along with prospective opportunities for the synthesis and
application of nano-MOFs, which will help promote their uses in multidisciplinary research.

1. INTRODUCTION specific design of hollow-structured materials can give an entire

Metal−organic frameworks (MOFs) are produced by the raft of good elements. In the late 1990s, MOFs became a fast-
formation of chemical bonds between organic ligands as linkers growing research field, pioneered by Omar Yaghi at UC
Berkeley. More than 90 000 MOF structures have been
and metal ions as nodes, leading to generation of periodic
reported, and the number increases regularly.6 MOFs are
network crystalline structures with high porosities and large
absorbent structures designed by the coordination between
surface areas, which promote their potential applications in
metal ions and organic linkers.
various fields of science and technology.1 In recent years,
MOFs are constructed through entrenching a metal ion with
absorbent materials, zeolites, and MOFs have earned
organic linkers by coordination (Figure 1), giving unfolded
significant consideration in chemical sciences for various
frameworks that exhibit the central vision of endless porosity, a
applications including energy, sensing and gas storage. The
reliable framework, a large pore volume and large surface area.
fascinating aspect is the porous property of MOFs, which
The permeability is the outcome of an extended organic unit
permits dispersion of recipient particles into a mass structure.
that offers an immense storage area and countless adsorption
The pattern and size of pores administer a choice of pattern
places. Also, MOFs withstand the potentiality to methodically
and size to accommodate guests.2 MOFs have a flexible design,
diversify and functionalize their pore structure.7
which offers vast structural variety and broad capabilities to
MOFs comprise both organic and inorganic components.
form objects with customized properties.3 They offer an
The organic components (bridging ligands/linkers) include a
ultimate high porosity, a large internal surface area, structural conjugate base of a carboxylic acid or anions, such as
tailorability, crystallinity, functional diversity, and versatility.4 organophosphorus compounds, salts of sulfonic acid, and
MOFs exhibit a typically wide inner surface area (frequently heterocyclic compounds as shown in Figure 2. The inorganic
500−7000 m2/g), structural flexibility, tunable porosity,
variable organic functionality, and physical/thermal stability,
making MOFs a materializing contender to conventional Received: August 18, 2022
permeable materials, such as activated carbons and zeolites.5 Accepted: November 14, 2022
MOFs have remarkably large internal surface areas due to their Published: December 2, 2022
hollow structure. The interactive effect of arrangements and
structures is governed by the physicochemical properties of the
constituents. MOFs are attractive illustrations of how the
© 2022 The Authors. Published by
American Chemical Society https://doi.org/10.1021/acsomega.2c05310
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Figure 1. Formation of MOF structure by formation of chemical
bonds between the metal ions as nodes and the organic molecule as a
linker.
elements are metal ions or clusters called secondary building
units (SBUs).8 The geometry of the MOFs is considered
Figure 2. Organic molecules as linkers used for the preparation of MOFs.
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through ligancy, the analytic geometry of the inorganic
components (metal ions), and the organic functional group
character. MOFs have been shown to include a variety of
shapes, including triangles with three points, square paddle
wheels with four points, trigonal prisms with six points, and
octahedrons with six points as shown in Figure 3. On a basic
level, the organic linker (ditopic, tritopic, tetratopic, or
multitopic ligands) responds to the metal ion by means of
more than one labile or vacant position. The ultimate
framework is reigned over via both the metal ion and the
primary building unit (PBU).2
The metal ion and bridging ligands might provide diverse
outcomes in an assortment of MOFs, customized for typical
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Figure 3. MOFs with various metal nodes and organic linkers.
applications.7 The enormous spaces of MOFs may bring about
the improvement of interpenetrating structures. In this way, it
is vital to prevent interpenetration by sensibly selecting the
PBU. The pore’s size is ensured, and the arrangement of the
spatial cavity can be managed by carefully selecting the metal
center and organic linkers and via varying the synthesis
conditions. MOFs are prepared by several approaches such as
solvothermal, microwave-assisted, ultrasonication, mechano-
chemical, electrochemical, ionothermal, and sonochemical
processing. The huge porosity permits their utilization in
separation and adsorption of gaseous molecules, micro-
electronics, catalysis, optics, bioreactors, drug delivery, sensing
applications, and so on. A fascinating and remarkable
development in this field is MOFs combined with functional
nanoparticles, resulting in novel nanocomposite materials with
exceptional characteristics and applications. Nanoparticle
composite MOFs have various chemical and structural
diversities, excessive loading capacity, and high decompos-
ability; thus, they are beneficial to traditional nanomedicines.2
In addition, MOFs and their composite materials have been
used as electrocatalysts for the ORR,9−11 carbon dioxide
reduction,12 the HER, and the OER.13,14 MOFs have so far
attracted a lot of interest in several research fields, both with
the aim of developing and synthesizing novel materials as well
as for a wide range of applications. In recent years, numerous
reviews of electrically conductive MOFs,15 2D MOFs,16 the
history of activation and porosity,17 clean energy applica-
tions,18 and so on have been published. In this article, we
provide a history of MOFs, their classification and the
nomenclature of MOFs (i.e., how to classify newly synthesized
MOFs from a historical point of view), synthetic approaches
for MOFs, and various influencing factors for the synthesis of
MOFs. Moreover, their potential applications in various fields
such as gas storage, drug delivery, electrochemical energy
conservation, and removal of water contaminants are
discussed. In addition, the advantages and disadvantages of
the synthesis approach for creating MOFs are emphasized. The
review comes to a close by outlining several crucial future
directions for the creation of nano-MOFs and their
applications.
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2. CLASSIFICATION AND NOMENCLATURE OF
METAL−ORGANIC FRAMEWORKS
2.1. Classification of MOFs. When combined with specific
materials, like metal oxides, quantum dots, carbon materials,
molecules, polyoxometalates, polymers, and enzymes, one can
prepare MOF nanocomposites that have functional diversity.
Depending on their component unit, MOFs could be divided
into a variety of groupings.19
2.1.1. Isoreticular MOFs. Isoreticular MOFs are synthesized
by [Zn4O]6+ SBU and a series of aromatic carboxylates. They
are octahedral microporous crystalline materials. In recent
years, for the advancement of sensors, IRMOF-3 has been used
abundantly. Zhu and co-workers synthesized nanosheets of
IRMOF-3 with magnificent sensitivity and selectivity toward
recognition of 2,4,6-trinitrophenol in wastewater.20,21
2.1.2. Zeolitic Imidazolate Frameworks (ZIFs). Zeolitic
imidazolate frameworks are synthesized using various elements
that have valence electrons and imidazole derivatives. They are
zeolite topological structured materials. ZIFs comprise ZIF-8,
ZIF-90, ZIF-L, ZIF-71, ZIF-67, ZIF-7, etc.19 The ZIF-8
material is discussed beyond the diverse ZIF materials due to
its dominant performance, such as the sensitivity of the acid,
excessive surface area, lower cytotoxicity, immense pore size,
etc.22 Pan and co-workers designed a ZIF-8 MOF for detection
of the HIV-1 DNA.23 ZIFs have a huge pore size and superior
chemical and thermal stability that is used as a network to
develop novel MOF composites.24,25
2.1.3. Porous Coordination Networks (PCNs). Porous
coordination networks are stereo-octahedron materials, and
they have a hole−cage−hole topology with a 3D structure.
Some of the PCNs are PCN-333, PCN-224, PCN-222, and
PCN-57.19 One of the PCN MOFs, PCN-222 MOF, is
extensively applied in sensors. Ling et al. synthesized a
susceptible electrochemical sensor to detect DNA by using
PCN-222.26
2.1.4. Materials Institute Lavoisier (MIL) MOFs. Materials
Institute Lavoisier MOFs are synthesized using various
elements that have valence electrons and an organic compound
containing two carboxylic functional groups. The pore size
arrangement of MIL MOFs could be converted freely under
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outward incitement. MIL MOFs contain MIL-101, MIL-100, 1,58 are used to categorize the research teams that created the
MIL-53, MIL-88, MIL-125, etc.19 Zhang and co-workers MOFs. Table 1 provides examples of the MOFs and their
prepared MIL-101(Cr) through a hydrothermal approach to abbreviations.
make resistive humidity sensors with elevated sensitivity.27
MIL composites are used as chemical sensors to immobilize Table 1. Illustrations of MOF Terms
proteins, QDs, and other constituents.28−30 Importantly, MILs
exhibit several unique features such as ultrahigh surface area, terms abbreviation ref
uniform pores and permanent porosity, exploring them as ideal MOF-2 MOF 44
candidates for various applications in biomedical and environ- MOF-5 45
mental sciences. Transfer capacity is the structure that prolong MOF-74 46
between micropores and mesopores under impassion of the UiO-66 University of Oslo 47
exterior influences. UiO-67 48
2.1.5. Porous Coordination Polymers (PCPs). Porous IRMOF-1 isoreticular metal−organic frameworks 49
coordination polymer materials are synthesized by carboxylic IRMOF-8 50
acid, pyridine, and its derivative as the PBU and transition ZIF-8 zeolite imidazolate framework 51
metal ions as the SBU.19 Ludi and co-workers first synthesized ZIF-10 52
the 3D network assembly of Prussian blue�a PCP.31 Hirai MIL-53 Materials Institute Lavoisier 53
and co-workers immobilized PCP Zn(NO2-ip)(bpy) on the MIL-88 54
surface of QCM to sense organic vapors.32 PCPs exhibit MIL-125 55
magnificent characteristics in biomacromolecule separation HKUST-1 Hong Kong University of Science and 56
(MOF-199) Technology
and heterogeneous catalysis.33,34 LIC-1 Leiden Institute of Chemistry 57
2.1.6. University of Oslo (UiO) MOFs. A University of Oslo MOP-1 metal−organic polyhedra 58
MOF based on dicarboxylic acid as the PBU and Zr6(μ3- CPL-2 coordination polymer with pillared layer 59
O)4(μ3-OH) as the SBU was first synthesized by Lillerud and framework
co-workers.35 UiO-66(Zr) was constructed by a solvothermal F-MOF-1 fluorinated metal−organic framework 60
method from ZrCl4 and BDC with octahedral and tetrahedral
pore cages.35 UiO-66 had superior thermodynamic stability,
and the experimental results showed that the framework is
stable at pH = 14. UiO-66 has been successfully used as a 3. SYNTHESIS OF MOFS
supercapacitor electrode material.22 As discussed before, MOFs are comprised of two significant
Furthermore, based on the aforementioned classification, components: the metal ion and the organic ligands or bridging
numerous MOFs, such as, Northwestern University (NU),36 linkers. Formally, MOFs are created by mildly mixing metal
Pohang University of Science and Technology (POST-n),37 ions with organic linkers to create porous and crystalline
Dresden University of Technology (DUT-n family),38 materials. During the last couple of decades, different
University of Nottingham (NOTT-n),39 Hong Kong Uni- preparation schemes have evolved and been applied to prepare
versity of Science and Technology (HKUST-n),40 and MOFs. These are classified as conventional solvothermal
Christian-Albrechts-University (CAU-n family), 41 have methods, unconventional methods, and alternative methods.61
emerged in recent years. Biological metal−organic frameworks 3.1. Microwave-Assisted Method. Microwave-assisted
(Bio-MOFs) are a novel class of permeable materials that has approaches have been broadly applied for the rapid synthesis of
emerged recently.42 MOFs under hydrothermal conditions. With the help of the
2.2. Nomenclature of MOFs. Recently, various constitu- microwave process, small metal and oxide particles are
ents which consist of metal ions linked to organic linkers have produced.62 It provides an efficient way of heating and is
been reported. These materials are known by various names: derived from the interactivity between the electromagnetic
metal−organic frameworks, hybrid organic−inorganic materi- waves and the mobile solvent charges, like polar solvent ions or
als, metal−organic polymers, coordination polymers, and molecules. This approach is mainly used in organic chemistry
organic zeolite analogues.3 The word MOF illuminates the and has been extensively used to prepare nanosized metal
presence of an absorbent structure as well as a strong bond oxides.63 To design metal nanosized crystals, the temperature
responsible for the rigidity of the framework with a distinct of the solution could be elevated through microwaving for 24 h
geometry where secondary structural units can be replaced or more (Scheme 1). In this approach, a substrate mixture with
throughout the synthesis procedure.43 The MOF abbreviation an appropriate solvent is put in Teflon vessel, and the vessel is
is generally used as a common name of the class of compound; sealed and positioned in the microwave for adequate
when it is followed by an ordinal number, it indicates a specific temperature and time. The task of the microwave is to convert
MOF.44−46 Exploring a wide number of structures and MOF the electromagnetic energy into thermal energy, in which the
properties facilitates formulation criteria for the design of permanent dipole moment of the molecules is connected with
framework structures with impulsive characteristics, for an applied electric field, which rapidly heats the liquid
example, with similar symmetry IRMOF-1 and IRMOF- mixture.64 Polar molecules in a substrate mixture attempt to
8.49,50 Many MOFs are named not as reported by the align themselves in an electromagnetic field and an oscillating
similarity of their structure but as reported by the place of their field, changing their orientations permanently as a result.
finding, like UiOs,47,48 MILs,53−55 HKUST,56 LICs,57 etc. Applying the right frequency will cause molecules to collide,
Furthermore, a huge family of MOF is the zeolite imidazolate raising the temperature of the system and the system’s kinetic
framework in which transition metals (Zn, Fe, Cu, Co, etc.) are energy. Due to the radiation interacting directly with the
bonded through N2 atoms and linked with imidazole rings.51,52 solution or reactant, it is a particularly energy-efficient way of
Several designations, such as CPL,59 F-MOF-1,60 and MOP- heating. Consideration should be paid to the choice of solvent
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Scheme 1. Microwave-Assisted Synthesis of MOF Structures
Scheme 2. Electrochemical Synthesis of MOF Structures
Scheme 3. Conventional Solvothermal Synthesis of MOF Structures
and particular energy input,65 resulting from uniform size
nanocrystals. Microwaves with frequencies between 300 and
300 000 MHz are a sort of electromagnetic radiation.63
Microwave-assisted MOF synthesis is mainly focused on
rapid crystallization and formation of nanoscale products to
enhance product purity for the particular synthesis of
polymorphs.65
3.2. Electrochemical Method. The electrochemical
method is used for the rational construction of a vast number
of MOFs. HKUST-1 was first synthesized by BASF in 2005
through the electrochemical method.69 Their primary aim was
to isolate anions like chloride, perchlorate or nitrate
throughout the synthesis procedure, thereby avoiding the
formation of corrosive anions (nitrate and chloride), which can
be considered that electrochemical method is a green
chemistry approach for MOFs preparation bother to extensive
construction procedures. Since the synthesis is carried out in
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the absence of any metal salts, the formation of any corrosive
anions like nitrate and by-products are avoided, making the
deposition environment friendly. The key component of this
technique for MOF synthesis is that metal ions are added
through an electrochemical procedure rather than through a
solution of the corresponding metal salt or by production of
these ions following a metal’s reaction with acid.65 The
electrochemical method of MOFs uses electrons as a source of
metal ions that are passed through a reaction mixture, which
contains dissolved organic linker molecules and an electrolyte
via anodic dissolution as the metal source instead of metal
salts.62 The electrode is placed in a solution that contains PBU
and frequently contains an electrolyte. By giving a suitable
voltage, the metal is dissolved and the metal particles essential
for the development of MOFs are present exterior to the
electrode’s surface. The metal ions instantly respond with the
organic linker present in solution, and the MOF is designed
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Scheme 4. Mechanochemical Synthesis of MOF Structures
Scheme 5. Sonochemical Synthesis of MOF Structures
near the electrode surface (Scheme 2). By using a protic
solvent, the metal deposition on the cathode escapes; however,
H2 is produced. The electrochemical route is too feasible to
run a consistent procedure to acquire a higher solid content
than the ordinary batch reaction.70
3.3. Solvothermal Method. The solvothermal method
has been widely used for the preparation of MOFs. This
technique is employed due to its simplicity, convenience of
usage, crystallinity, and high yield. In this approach, metal salts
and organic ligands are stirred in protic or aprotic organic
solvents which contain the formamide functionality.73 Aprotic
solvents include DEF, DMF, NMP, DMSO, DMA, acetonitrile,
and toluene. Protic solvents are methanol, ethanol, and mixed
solvents. To keep away from the issues associated with the
distinct solubility of the initial components, mixtures of
solvents can be used. If water is used as a solvent in MOF
synthesis, it is referred as the hydrothermal method.70 This
mixture is poured into the closed vessel at elevated pressure
and temperature for several hours or a day. Glass vials are used
at low temperature, and a Teflon-lined stainless-steel autoclave
is used for high temperature (>400 K) in the reaction (Scheme
3). Then, the closed vessel is heated at a temperature greater
than the aprotic or protic solvent’s boiling point to bring about
higher pressure.73 The chief parameter of this reaction mixture
is the temperature, and there are two temperature ranges, i.e.,
the reaction taking place in a closed vessel above the solvent’s
boiling point under autogenous pressure referred to as a
solvothermal reaction, and a nonsolvothermal reaction
happens below or at the boiling point of the solvent under
ambient pressure.74 Due to the high pressure, the solvent is
heated above its boiling point and the salt will melt, which then
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aids the reaction. In addition, to acquire a large crystal with a
high internal surface area, slow crystallization from a solution is
required.
3.4. Mechanochemical Method. Mechanochemistry
concentrates on responses between solids usually for the
most part started just using mechanical energy. A combination
of a metal salt and an organic ligand is ground in a ball mill or
with a mortar and pestle in the absence of solvent; then, the
ground mixture is heated mildly to evaporate other volatile
compounds and H2O, which formed as a byproduct in the
reaction mixture.61 The mechanochemical approach for the
preparation of MOFs is an easier method than the other
methods (Scheme 4). In mechanochemical synthesis, chemical
transformation takes place through mechanical breaking of
intramolecular bonds.79 This reaction exists at room temper-
ature, and organic solvents can be avoided. The first MOF
synthesis through this approach was reported in 2006.80
Currently, this method is used on a large scale for the
preparation of various kinds of MOFs.
3.5. Sonochemical Method. Recently, the sonochemical
method has been used for rapid synthesis of MOFs as it
decreases the time for crystallization through ultraradiation. In
this method, a cyclic mechanical vibration (from 20 kHz to 10
MHz) is used for the synthesis of the MOF.83 In a horn-shaped
Pyrex reactor with a sonicator bar and a variable power output,
a mixture of the metal salt and organic linker is added without
the use of external cooling62 (Scheme 5). The main factor for
the cavitation’s impact on a liquid is ultrasonic. Cavitation is
the name for the development and collapse of bubbles created
in a solution after sonication. It produces very fine crystallites
at very high temperatures of about 5000 or 4000 K and high
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Table 2. Overview of Various Synthetic Routes (Microwave, Electrochemical, Solvothermal, Hydrothermal, Mechanochemical,
and Sonochemical) for the Preparation of MOFs
method MOFs metal salt organic ligand reaction conditions ref
microwave-assisted method MIL-100(Fe) FeCl3·6H2O H3BTC 66
Fe-MIL-53 FeCl3·6H2O H2BDC 80 W, 5 min at 50 °C 67
Hf-UiO-66 and Zr-UiO-66 HfCl4 and ZrCl4 H2BDC 90 W, 3 min 68
electrochemical method MOF-199 Cu electrode H3BTC electrolyte: TBATFB, 12 V for 1.5 h 71
Al-MIL-100 Al(NO3)3·9H2O H3BTC electrolyte: KCl, 50 mA, 333.15 K 72
solvothermal method Eu−MOF Eu (NO3)3 ·6H2O H3TATAB 72 h at 120 °C 75
MOF-5 Zn(NO3)2·6H2O H2BDC 4 h at 120 °C 76
hydrothermal method NH2-UiO-66 ZrCl4 2-amino terephthalic acid 24 h at 120 °C 77
Cr-MIL-101 Cr(NO3)3·9H2O H2BDC 8 h at 220 °C 78
mechanochemical method MOF-74 Mg(NO3)2·6H2O H4dobdc 5 min 81
MIL-78 yttrium hydride trimesic acid 82
sonochemical method MOF Zr−fum ZrOCl2·8H2O fumaric acid 30 min 85
[Zn2(oba)2(bpy)] Zn(NO3)2·6H2O H2oba, bpy 60 min 86

Figure 4. Merits (in green) and demerits (in red) of various synthetic routes for preparation of MOFs.

pressures of 1000 bar. In 2008, sonication was used for the first
time for the synthesis of MOFs.84 Table 2 provides examples
of MOFs prepared by various synthetic routes (microwave,
electrochemical, solvothermal, hydrothermal, mechanochem-
ical, and sonochemical methods).
Apart from these, other methods such as the diffusion
method, spray-drying synthesis, ionothermal synthesis, and
chemical vapor deposition have been used for the synthesis of
MOFs.87 In the spray-drying method, atomization of a solution
consisting of MOF precursors into a microdroplet spray is
performed using a two-liquid nozzle. The process injects one
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or more solution in the inner nozzle at a definite speed (feed
rate). The outer nozzle compresses air or nitrogen at another
constant speed (discharging rate). Then, each atomized
droplet is heated at a specific temperature through a gas and
starts to evaporate. Solvent evaporation increases the
precursor’s concentration at the surface until large particles
of MOFs begin to form.88 The diffusion method is divided into
two phases: (i) gas-phase and (ii) liquid/gel-phase diffusion. In
this method, diffusion of one of the reagents has a controlled
reaction rate. Gas-phase diffusion consists of an organic ligand
solution with a low boiling point being used as the solvent. In
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liquid-phase diffusion, the metal ion and organic ligand are
dissolved in immiscible solvents. In the gel-phase diffusion
method, the metal ion and organic ligand are dispersed in a gel
substance and crystallization begins. This method is often
performed under moderate conditions but is a time-consuming
reaction.70 In ionothermal synthesis, an ionic liquid acts as
both the solvent and the structure-directing agent. Here, an
ionic liquid is used as a charge balance group, structural
template, or reaction medium. Thus, the ionothermal method
provides a pure ionic environment. The physicochemical
characteristics of MOFs can be measured by altering the
composition of the ionic liquid. Some merits of this method
are a lower melting point, good thermal stability, and varied
liquid range.89 CVD is also known as a solvent-free method
which is used to make crystalline materials in the semi-
conductor industry. This method has two steps: in the first
step, atomic layer deposition via vaporized metal and oxygen
or water precursors forms a metal oxide thin film, and in the
second step, vaporized ligand sources are introduced to
transform the metal oxide film and crystals begins to form.90
However, each MOF synthesis has some merits and demerits.
The solvothermal method is a one-step synthetic approach that
gives single crystallinity at a moderate temperature.91 On the
other hand, this method takes a long period of time, requires
more solvents, and produces acids as byproducts.92 In the
microwave-assisted method, MOFs are generated with a
uniform morphology by means of rapid crystallization in less
time and also give a high yield in particular phase purity. It is
challenging to change the reaction conditions by controlling
the irradiation power. Reproducibility is eventually hindered by
the inability of the many instruments to simulate the same
variables; as a result, the temperature and reaction time are also
limitations of the microwave-assisted method.93,94 The electro-
chemical method generates more solids compared to the batch
process and can be applied as an industrial approach to form
MOFs.95 It has been noted that the MOFs produced by the
electrochemical method are of lower quality since the linker
molecules and/or conducting salt were included in the pores
during crystallization.96 There are numerous reasons to be
interested in mechanically activated MOF synthesis. Environ-
mental concerns are thus one of the important points.
Reactions can be performed with solvent-free conditions at
room temperature, which is particularly helpful in situations by
avoiding organic solvents. It is possible to produce MOFs with
few components and to achieve quantitative yields in a short
amount of time.97 Moisture is the main challenge in the
synthesis of MOFs via the mechanochemical method. Single
crystallization and a lower pore size are limitations of the
mechanochemical method.98 Sonochemical synthesis in MOF
chemistry is developing a technique that is rapid, energy
efficient, eco-friendly, simple to use, and operable at room
temperature.99 Crystal decomposition happens during the long
reaction time of the synthesis of the MOFs.100 Currently,
particular attention is given to the synthesis of MOFs to step
up the crystallization of MOFs by rapid reactions. Merits and
demerits of various synthetic approaches for the preparation of
MOFs are described in Figure 4.
4. INFLUENCING FACTORS FOR SYNTHESIS OF MOFS
The synthesis of MOFs has been affected by several exterior
factors, such as the selection of organic ligands, metal ion salts,
molar ratio, pH, solvents, and temperature of the reaction
media.101 Organic ligands can be categorized into a number of
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types based on their coordinating groups, including carboxylic
acid-based linkers, nitrogen-containing heterocyclic, phosphor-
yl, and sulfonyl linkers, cyano linkers, etc. Carboxylic acid-
based linkers are among the different organic linkers, and they
are frequently chosen as multifunctional organic linkers as they
have many coordination nodes to act as H-bond acceptors and
donors to metal ions, which allow for a variety of structural
topologies to assemble MOF structures.102 Heterocyclic linkers
that contain an N atom have distinct coordination patterns,
which increase the target compound’s capacity to be controlled
structurally.103 For the fabrication of novel MOF structures,
mixed linkers are another option for creating new MOFs that
have novel structures.104 One of the typical methods to
produce higher dimensional networks is to extend the metal
carboxylate complexes with a second bridging ligand. More-
over, the structure of MOFs may be significantly impacted by
the positional the isomerism of ligands with the same
coordination groups but located in different places. For
instance, the aromatic dicarboxylic acids H2IPA and H2TPA
both have the tendency to bind and are engaged in controlling
the MOFs’ structural assembly.105 The linker L combined with
these two linkers to form {[Zn(L)(IPA)]}n and {[Zn(L)-
(TPA)]·DMF} n complexes with the Zn 2+ metal ion,
respectively, via the solvothermal method. The H2IPA linker
combines with L and forms 1D chains of {[Zn(L)(IPA)]}n,
and the H2IPA is replaced by H2TPA, which forms a 3D
structure of {[Zn(L)(TPA)]·DMF}n. The selection of the
metal salt plays a significant role in the synthesis of MOF
structures. Salts utilized as metal sources can be divided into
two categories: inorganic acid salts and organic acid salts. Most
of the inorganic salts used are carbonates, sulfates, and nitrates,
and the organic salts are mostly acetates and their
derivatives.106 For instance, [Cu3(btc)2] was prepared by
using two different metal salts Cu(OAc)2 and Cu(NO3)2 and
H3BTC as the organic linker. The result revealed that
Cu(OAc)2 was favorable for the preparation of [Cu3(btc)2]
with a high surface area.107 In addition, by adjusting the metal
ions and the coordination modes of the organic ligands, it is
possible to predict the topology of the MOFs; also, the stability
of the MOF is generally improved by the presence of
numerous metal ions that are connected by various
coordinating ligands. The metal ions serve as the MOF’s
construction node and have a direct impact on the structures
of MOFs through their coordination geometry. In the synthesis
of MOFs, the concentration of the precursors (molar ratio) is
also a significant factor. The topological patterns of MOFs are
mostly dependent on the ratio of metal ions and organic
linkers.101 Liu and co-workers explored the effect of the metal
to linker molar ratio on the synthesized MOF structure by
using CoCl2 and btze.108 The result showed that the initial
materials with a molar ratio of Co(II)/btze of 1:1 or 1:1.5 form
2D [Co(btze)2(SCN)2]n MOFs. When they used a molar ratio
of 1:2 or more btze linker, a 3D [Co(btze)2(SCN)2]n MOF
structure resulted. Various coordination modes can be adopted
by organic linkers at different pH ranges.109 Moreover, as the
pH value rises, the linker deprotonates to a greater extent. For
example, by raising the pH, the Al3+ ion coordinates with 4, 6,
and 8 −COOH groups, yielding MIL-121 (at pH 1.4), MIL-
118 (at pH 2), and MIL-120 (at pH 12.2), respectively.110
Spectroscopic data revealed that MOFs are formed with an
interpenetrated network at higher pH and were uninterpene-
trated at a lower pH.111 The color of the MOF compounds
also depends on the pH of the reaction medium. Luo and co-
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Figure 5. Influence of solvent systems on the morphology of the MOF. Reproduced with permission from ref 115. Copyright 2011 American
Chemical Society.
workers, via their experimental work, analyzed three Co−MOF
complexes, viz. [Co2(L′)(HBTC)2·(μ2-H2O)·(H2O)2]·3H2O
(1), [Co3(L′)2·(BTC)2]·4H2O (2), and [Co2(L′)·(BTC)·(μ2-
OH)·(H2O)2] ·2H2O (3), which different structures and
colors upon varying the pH.112 These three MOFs also showed
different adsorption capabilities. It is also known that materials
of higher dimensions are formed at higher pH.113
The solvent plays a significant part in the synthesis of MOFs
and also in morphology determination of the MOFs. Solvents
are coordinated through metal ions as a structure-directing
agent. In view of this, solvents with a polar nature and higher
boiling points are widely used in MOF synthesis. Generally,
solvents like DEF, DMF, DMSO, DMA, acetone, alcohol,
acetonitrile, etc., are used.114 The MOF preparation process
was affected by the reaction medium due to the solubility,
solvent polarity, and protolysis behavior of the organic ligand.
The different solvents in the same reaction conditions provide
different morphologies.61 Banerjee and co-workers reported
MOFs containing magnesium and PDC having various crystal
structures prepared under the same conditions using different
solvents115 (DMF, H2O, EtOH, and MeOH) (Figure 5). They
found that the MOF network’s dimensionality is determined
by the solvent’s capacity to coordinate with the metal. Among
them, H2O has the highest attraction toward Mg, whereas
other solvent mixtures (EtOH:H2O and DMF:MeOH) did not
coordinate with the metal centers, signifying that the use of
water as a solvent greatly influenced formation of covalent
bonds with the metal ions.
The temperature is another critical factor which affects the
characteristics of the synthesized MOFs. Due to the reactant’s
good solubility and the production of large crystals with high
superiority, the material exhibits a high crystallization nature at
high temperatures. The temperature of the reaction mixture is
affected by the nucleation and crystal growth rates. On varying
the reaction temperature, the morphology of the MOF is
significantly changed, which allows one to use them for
different applications.61,116 To support this, monoclinic and
triclinic morphological Tm−succinate MOFs have been
successfully synthesized at diverse temperatures using the
same empirical formula.117 Bernini and co-workers investigated
the thermal stability of Ho−succinate MOFs prepared via the
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hydrothermal approach at higher temperature and at room
temperature, illustrating that a Ho−succinate MOF prepared
via the hydrothermal approach is more thermally stable than a
Ho−succinate MOF prepared at room temperature.118
5. APPLICATION OF MOFS
In MOFs, there are three properties acting simultaneously,
namely, the crystalline nature, porosity, and presence of strong
metal−ligand interaction. A rare combination of these
properties makes MOFs an exceptional class of materials.
The high surface area, small density, structural flexibility, and
tunable pore functionality of MOFs makes them useful in a
broad range of intending applications, such as in gas storage
and delivery, drug delivery, rechargeable batteries, super-
capacitors, separation membranes, catalysis, sensing, etc.119
5.1. Gas Storage and Delivery. Due to the unique
structure of MOFs, the key application is gas storage because
of their large surface area and absence of dead volume.120 This
outcome could be noticeable and relies on the pressure,
temperature, and type of gas used. The MOF material also
plays an important role for this application. Energy-oriented
smart applications of MOFs are hydrogen and methane
storage, carbon dioxide capture, and nitrogen adsorption.121
Molecular hydrogen has more energy than any fuel. The
storage and movement of hydrogen gas needs a large amount
of energy compression and liquefaction processes due to the
very low energy density. MOFs draw attention as a result of
their high surface area, surface to volume ratios, and chemically
tunable structures.122 A gas cylinder with a MOF material
could store more hydrogen at a specified pressure in
comparison to an empty gas cylinder because a molecule of
hydrogen adsorbs on the MOF surface.
As MOFs have no dead volume, there is no loss of storage
capacity as an outcome of space blocking by an inaccessible
volume. When the hydrogen is in the gaseous state, MOFs
provide optimum benefits of storage capacity, which is
restricted in the liquid state.123 The magnitude of gas that
can be adsorbed to the MOF surface relies on the pressure and
temperature of the gas. Typically, the adsorption rises when
the temperature decreases and the pressure increases
(maximum 20−30 bar, after this the capacity of adsorption is
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reduced). Férey’s group reported a hydrogen capacity of 3.8 wt
%, i.e., MIL-53, which is obtained by using aluminum salts and
1,4-benzene dicarboxylic acid.124 A 2.0 wt % hydrogen storage
capacity was reported by Kim and Seki derived from pillaring
with secondary amine linker (triethylenediamine) at 87 K and
1 bar. Similar values were attained by MOF-505 by Yaghi’s
group in which Cu metal is bound by 3,3′,3,5′-biphenyl
tetracarboxylic acid. A zinc MOF made with NTB linker may
absorb 1.9 wt % of hydrogen at 77 K.125 Hydrogen storage
data are recorded up to 7.5 wt %, i.e., MOF-177, at 90 bar.126
However, to date, it is uncertain whether high surface area
MOFs like MOF-100, MIL-177, and MOF-5, compounds with
a moderate surface area of between 1000 and 1500 m2 g−1,
isoreticular compounds, or a uniform small pore size MOF will
be the most favorable storage medium.121 However, a
comparison with NaX-zeolites evidently shows the best nature
of MOFs on conventional microporous inorganic media.127
MOF-177 shows maximum favorable results for the storage of
hydrogen (7.5 wt % at 77 K up to 40 bar). The two main
schemes directing the MOF’s design for hydrogen storage are
(i) to expand the theoretical storage capability of the MOF
materials and (ii) to carry out working situations nearer to the
surrounding pressure and temperature.126
5.2. Biomedical Applications. In the key area of health
there are many therapeutic disadvantages of APIs, i.e.,
unfavorable solubility and stability, less bioaccessibility, short-
term half-life, and restricted bypassing of biological barriers;
because of these reasons, their therapeutic uses are primarily
finite. In drug delivery, promotion of an effective drug delivery
system is one of the dominant areas of research which ensures
a favorable result by using safe carrier materials.128 To date,
numerous transit materials have been accounted for and
structured in various forms, such as carbon dots,129 nano-
emulsions,130 hydrogels,131 micelles,132 liposomes133 etc. Yet, a
greater number of transit materials frequently have low drug
loading capacities, intolerable toxicity, unbound release, and an
unstable morphology. To overcome these difficulties, MOFs
are investigated as carriers for conveying loaded cargoes to
admired sites due to their plausible size, composition, and
functionalized pore surface.134 MOFs as feasible drug delivery
materials have the following unique advantages: (i) excessively
adjustable properties and pore size, (ii) elevated drug loading
capacity, and (iii) manageable multifunction.128 The MIL
group is a favorable class of MOFs for drug delivery which is
acquired from trivalent metal ions and carboxylate linkers,
offering a huge pore size (24−25 Å) and applicable surface
area (3100−5900 m2/g). For example, MIL-53(Fe) and MIL-
53(Cr), two typical MOFs, have been reported to load
ibuprofen (IBU) up to 17.4% and show an extended release
time of 21 days in simulated body fluid (Figure 6).135 MIL-
53(Cr) was prepared by using Cr(NO3)2 and benzene 1,4-
dicarboxylic acid, whereas MIL-53(Fe) was synthesized from
FeCl3 and benzene 1,4-dicarboxylic acid via a hydrothermal
approach.
In this survey study, MIL-53(Fe) had optimum loading
capacities of 14 wt % for busulfan and 30 wt % for caffeine.
MIL-100(Fe) is also used in drug delivery. Some drugs such as
azidothymidine triphosphate (21.1%), DOX (9.1%), cidofovir
(16.1%), caffeine (24.2%), and IBU (33%) can successfully
load by MIL-100.
5.2.1. Strategies of Drug Loading. There are primarily 3
sorts of drug loading strategies: one-step encapsulation (in situ
encapsulation), postsynthesis encapsulation (ex situ encapsu-
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Figure 6. Releasing study of IBU from MIL-53(Cr) and MIL-53(Fe).
Reproduced with permission from ref 135. Copyright 2008 American
Chemical Society.
lation), and acting as an active molecule in a linker process.
Typically, the ex situ encapsulation method is too complicated
and time consuming, as stirring the active MOFs and drug for a
few days is essential while loading it. However, due to its
reliable loading rate, it is still a frequently used method. The
one-step encapsulation process has been used for few
thermostable drugs and certain MOFs because of the deficient
heat stability of the drug and in high concentration drug
solution it is difficult to synthesize MOFs.128 Liedana and co-
workers discovered two methods for encapsulating caffeine
into ZIF-8.136 Here, ZIF-8 was prepared from Zn(NO3)2 ·
6H2O and 2-methylimidazole and the CAF@ZIF-8 IN was
prepared via the one-step encapsulation method. The caffeine
was encapsulated inside the pore of ZIF-8. According to TGA
(Figure 7a and 7b), in the ex situ process (CAF@ZIF-8 EX)
the contact time was prolonged at 80 °C for 8 h (4.2 1.4%)
and in the in situ process (CAF@ZIF-8 IN) the contact time
was set at 25 °C for 2 h, resulting in a caffeine load of 28.1 ±
2.6%. Also, to reach a similar result, the contact time must be
prolonged about 3 days as t the in situ process was 25 wt % at
80 °C. Furthermore, the crystallinity of the material could be
damaged due to a longer encapsulation time.128,136 The UV
absorption investigation exhibited only caffeine released from
CAF@ZIF-8 EX (8 h) after 3 days; however, it was constantly
released from CAF@ZIF-8 IN and CAF@ZIF-8 EX (3 days)
for 27 days. Lijia and co-workers fabricated an iron-based
MOF MIL-101-C4H4 for the encapsulation and release of
DOX.137 First, they prepared MIL-101-C4H4 by using FeCl3
and 1,4-naphthalene dicarboxylic acid through a microwave-
assisted method. Then, DOX was added dropwise into the
MIL-101-C4H4 in an alkaline medium. The DOX was
encapsulated in the pores of MIL-101-C4H4, and the loading
capacity was 24.5 wt %, which was completed with a loading
efficiency of up to 100% (Figure 7c and 7d).
In the third strategy, the MOF depends on the active
molecular ligands having high loading capacities to avoid
toxicity compared to inactive molecular ligands, and these
MOFs could simply reach the combination with the drug by
loading another drug.128 Zn−MOFs with ligand ferulic acid
have been used as in vitro drug carriers for 5-FU.138 The
maximum loading capacity of 0.388 g/g was achieved when
desolvated MOF was immersed in a 5-FU ethanol solution at a
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Figure 7. (a) TGA plot of one-step and ex situ encapsulation of caffeine in ZIF-8. (b) UV absorption of caffeine delivery from CAF@ZIF-8_EX (8
h), CAF@ZIF-8_EX (3 days), and CAF@ZIF-8_IN in water. Amount of encapsulated caffeine as measured by TGA and UV is shown in the inset
table. Reproduced with permission from ref 136. Copyright 2012 American Chemical Society. (c) Schematic representation of DOX-MIL. (d)
Loading capacity and loading efficiency of DOX to MIL-101. Reproduced with permission from ref 137. Copyright 2021 American Chemical
Society.

weight ratio of 1:3 for 2 days. Ferulic acid was liberated when
5-FU was released due to the degradation of MOF. A pH-
dependency phenomenon was shown by the release of ferulic
acid and 5-FU at the same time, which showed that 5-FU was
delivered with degradation of {[Zn2(fer)2]}n.
5.2.2. pH-Responsive Drug Delivery Systems. Conven-
tional cancer treatment methods restrict the use of chemo-
therapy in clinics due to its high toxicity and poor absorption
of anticancer medicines.139 The selectivity of an anticancer
drug is responsible for the side effects of chemotherapy.
Miserably, most of the conventional formulation cannot
differentiate between healthy tissue and cancerous tissue in
the body. The pH of the physiological nature in cancer tissues
was minor compared to that in ordinary tissues.140 Therefore, a
pH-responsive drug delivery system was preferred and suitable
for cancer therapy. The pH range of this delivery system is
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from 4 to 6. By a pH-responsive DDS, the drug molecule can
be released in the tumor region only. Such a system permits
rapid and effective drug release inside the cancerous cells
without harm to normal cells and hence decreases the systemic
disadvantages of chemotherapy in the human body. Therefore,
this pH-responsive DDS which has the controllable release
features of MOFs has been identified as favorable in a
therapeutic application.128 Adhikari et al. reported a feasible
process to encapsulate DOX into ZIF-8 (highly stable at
neutral medium) and analyzed its capacity for managed drug
release at different pH levels.141 Chowdhuri and co-workers
reported a rapid and simple method of an upconversion
nanoparticle (i.e., multifunctional nanoparticle) UCNP@ZIF-
8/FA to release 5-FU anticancer drug at different pH levels.142
Schnabel and co-workers recently reported Zn−MOF-74,
containing Zn2+ ions and the 2,5-dihydroxybenzene-1,4-
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Figure 8. Cyclic performance of a (a) carbon-containing Co3O4/Ti plate and (b) carbon-free Co3O4/Ti plate at high-rate current. Reprinted with
permission from ref 156. Copyright 2018 Elsevier.
dicarboxylate ligand, as a drug nanocarrier of As2O3.143 A high
amount of drug As(III) (153 mg of As2O3 in 1 g of drug-
loaded material) was absorbed into Zn−MOF-74; eventually,
the release process of As(III) shows an obvious pH-responsive
mechanism. At a temperature of 37 °C, As(III) drug-loaded
Zn−MOF-74 was dissolved in PBS, which has two different
pH values of 6.0 and 7.4. It was shown that As(III) release was
pH stimulated and occurred more quickly at a pH value of 6.0
than at a pH value of 7.4.
5.2.3. Magnetic Drug Delivery. Recently, magnetic nature
MOFs have found to be potential candidates for biomedical
applications due to high surface area and remarkable response
to magnetic field, faovring to store and release of target drug
molecules, which also to allows storing and releasing
pharmaceuticals, while the magnetic particles provide
sensitivity to a magnetic field. A magnetically responsive
drug delivery system permits conceivable excellence in
magnetic targeting, magnetic separation, magnetic hyper-
thermia, and MRI.144 Magnetic drug delivery is a classic tactic
to improve drug-loaded therapeutic potency.145 MDD is the
most promising targeted drug delivery system. With the help of
external magnetic conditions, the preparation of magnetic
drugs can be kept at a precise position.146 Magnetic properties
of MOFs allow them to use as highly potential candidates for
drug delivery and bioimaging applications developing contrast
agents in MRI also permit the magnetic formulation to possess
actual time observing because it can be used for bioimaging as
a contrast agent.147 Fe3O4/Fe2O3 and bimetallic alloys have
been extensively used as a conventional colloidal magnetic
nanoparticle. However, there were some unavoidable draw-
backs like poor loading efficiency, instability, and cytotoxicity
which restricted the drug delivery application. The customized
MOFs with an integrated magnetic component or coordina-
tion of magnetic nanoparticles were favorable substitutes in
MDD. It has been proved that magnetic MOFs nanoparticles
could precisely convey the drug molecules by physical
encapsulation or chemical bonding and shows acceptable
biocompatibility.148 Ke and co-workers discovered a Fe3O4@
MOF-5 core−shell nanomaterial fabricated by Fe3O4 magnet-
ite nanorods and a nanocrystal of MOF-MO-5.149 Then,
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nimesulide, an anticancer drug, was loaded into Fe3O4@MOF-
5. A 20 wt % loading rate was obtained. Furthermore, it was
revealed that within 11 days nimesulide was fully loaded into
physiological saline from Fe3O4@MOF-5. Guan and co-
workers150 discovered an in situ pyrolysis process for the
preparation of γ-Fe2O3@MOFs; the ferric triacetylacetonate
was encapsulated inside MIL-53(Al) and ZIF-8. Ibuprofen as a
standard drug was loaded into γ-Fe2O3@MIL-53(Al) and
released in three stages over the course of 7 days at 37 °C. In
the first stage, about 30% of the drug was quickly released in
the first 3 h; after that, during the next 2 days, 50% of the drug
was released; last, 20% of the residual drug was released over 5
days. It was concluded that γ-Fe2O3@MIL-53(Al) was a
favorable magnetic material for drug delivery.
5.3. Electrochemical Application. As a unit to form a
substance of two different materials, MOF composites have a
number of vivid execution and electrochemical applications
that MOFs cannot accomplish independently, including
batteries, sensing, supercapacitors, and catalysis. Due to the
diversity of the MOFs, their composites could enhance the
characteristics of the MOF and boost the development of
electrochemical applications.151 This is important for the
effective use of upright and sustainable energy as well as in the
market of transportable electronic and electric vehicles, urging
the expansion of energy storing materials, mainly electro-
chemical energy storage. In light of this, using nanomaterials to
store electrochemical energy has proven to be a successful
strategy. Nanosized active materials having mechanical and
electrical properties and a wide surface area are most likely to
imbue the space toward discernment of the forth coming
generation of energy storage device. To serve different
electrochemical energy storage purposes, many analyses have
been executed to look for better methodologies for synthesis of
the materials.152 Several functional materials with zero to two
dimensions combined with MOFs have extensive applications
in electrochemistry, while MOFs fabricated with 3D functional
materials have hardly been examined and discussed.152
5.3.1. Lithium-Ion Batteries. Thus far, LIBs have been
extensively engaged with a movable electrical apparatus,
merged power grids, and electric vehicles because of their
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merits of eco-friendly performance, having high density, being core−shell in LIBs as the anode.159 Fe3O4@MOF showed an
weightless, and having an extended cycle life, giving them elevated discharge capacity of 1001.5 mA h/g in the 100th
magnificent benefits as energy storage devices.151 cycle, which was superior to pure Fe3O4 (696 mA h/g), a
Nowadays, aside from graphite (due to the theoretical limit charge capacity of 993.7 mA h/g, indicating intense reversible
of 372 mA h/g), viable negative electrode materials and several capacity, and a good rate capacity of 492.2 mA h/g, showing
nanostructured materials like graphene composites, carbon prospect in LIBs.
nanotubes, transition metal oxides, etc., have been widely 5.3.2. Supercapacitor. Supercapacitors (SCs) are different
explored for applications of LIBs. MOFs have been studied as types of ideal energy storing devices with a high power energy
cathode, anode, and electrolyte materials for LIBs.153 Recent storage, longer cycle life, high power density, and excessive
advancements in lithium metal-based anodic batteries have packaging flexibility compared to conventional energy storage
received great attention and suggested that these power devices.160 The formation of the supercapacitor is like that for
sources have enormous potential for revolutionizing the a battery, in which two electrodes are separated by an ion-
electric vehicle and power grid industries.154 It has been permeable membrane. Figure 9a shows a schematic illustration
widely reported that N-doped carbon nanomaterials effectively
enhance the electrochemical characteristics of carbon materi-
als. A NSPC material was reported for the high performance of
Li-ion batteries using a facile and reliable approach.155 This
material may function as an anode and provide high-rate cycle
performance with a long cycle life. Simple grinding of a mixture
of polyacrylonitrile and sublimed sulfur (1:1 mass ratio) leads
to the N-rich S-doped porous carbon. The resulting NSPC had
an optimum initial Coulombic efficiency of more than 67% and
a notable high initial reversible capacity of 1096 mA h/g at a
0.1 A/g current density. A prolonged cycle life of over 1100
cycles with an exceptional cycle performance of 695 mA h/g
was observed at a relatively high current flow of 5 A/g. The
synergistic effect of heteroatom doping and many mesopores
with a significant amount of edge defects, which facilitate extra
lithium-ion storage, is responsible for the observed rapid
lithium-ion storage. Moreover, porous films of Co3O4 bound
with Ti nanowires were also reported for the anodic Li-ion
battery.156 The Co3O4 film was synthesized by the pyrolysis of
Co−MOFs, and further, it was anchored by the Ti nanowire
that effectively supplies a notable rate capability as an anodic
Li-ion battery. The homogeneous distribution of carbon in
Co3O4 films aids in efficient electron transit, allowing the films
to effectively discharge their capacitive potential. In addition,
the carbon-containing Co3O4/Ti plate performs superior (400
mAh/g at 20 A/g) to the carbon-free Co3O4/Ti plate (100
mAh/g at 20 A/g) (Figure 8a and 8b). A zero-dimensional
MOF composite SnO2@MIL-101(Cr) was reported to show
speed capability and peak cyclability of around 510 mA h/g
with a 0.1 C reversible capacity after 100 cycles.157 Here, high Figure 9. (a) Schematic representation of electron movement and
crystalline MIL-101(Cr) was formed by encapsulating with method of charging, fully charged, and discharging in SCs. Reprinted
SnO2, thereby forming SnO2@MIL-101(Cr) that exhibit with permission from ref 161. Copyright 2020 Elsevier. (b) Specific
capacitance of NiCo−MOF, Ni−MOF, and Co−MOF at different
excellent cyclability and rate capability for Li-ion battery current densities. Reprinted with permission from ref 165. Copyright
applications. A 2D MOF composite Fe−MOF/RGO was 2019 American Chemical Society.
synthesized by Shen et al. for reversible Li+ storage.158 At a 500
mA h g−1 current density and a voltage range of 0.01−3 V, the
composites Fe−MOF, Fe−MOF/RGO (5%), and Fe−MOF/ of the electron position and charging process in a super-
RGO (10%) had primary discharge−charge capacities of capacitor.161 EDLCs and pseudocapacitors are the two
2213/786, 2055.9/891.1, and 1889.9/750 mA h/g, respec- different forms of SCs (can store charges through a reversible
tively, representing 35.5%, 43.3%, and 39.7% of the initial Faradaic reaction). The electrostatic adsorption between the
Coulombic efficiency, respectively. The primary Coulombic surface of the conductive electrode and the electrolytes is what
efficiency of Fe−MOF/RGO (5%) was maximal because RGO drives the capacitive process in EDLCs. The overall
was coated on the Fe−MOF to escape instant interaction capacitance of pseudocapacitors is produced via redox
between the electrode and the electrolyte. Furthermore, the reactions, intercalation processes, and electrosorption, which
Fe−MOF/RGO (5%) composite was used as an anode that involves an electron charge transfer between the electrode and
showed maximum Li storage after 200 cycles with a 1010.3 the electrolyte.162
mAh/g reversible capacity. Among them, the Fe−MOF/RGO SCs have been broadly used in several research fields due to
(5%) electrode exhibited the finest rate capability, showing novel characteristics; thus, the general approval of the
RGO enhanced the rate performance and cycling stability. ultracapacitor has led to various methodologies to increase
Feng and co-workers reported 3D composites Fe3O4@MOF the performance. There have been new electrode materials
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Figure 10. (a) Performance of MOF membranes in filtering: membrane filtration theory. Reprinted with permission from ref 169. Copyright 2020
Elsevier. (b) Progesterone for MF adsorption at various starting concentrations. Reprinted with permission from ref 171. Copyright 2016 Elsevier.
(c) Performance of the produced membranes for dye rejection. Reprinted with permission from ref 175. Copyright 2017 Elsevier. (d) Flux vs time
for TFN and M-TFN2 NF membranes following KHI rejection. Reprinted with permission from ref 178. Copyright 2018 Elsevier. (e) Salt
rejection of TFC RO membranes. Reprinted with permission from ref 182. Copyright 2017 Elsevier. (f) FO performance of membranes. Reprinted
with permission from ref 183. Copyright 2019 Elsevier.

synthesized, surface electrodes have been modified, and hybrid
systems have been constructed.163 New types of MOFs with
the capacity for structural customization, excess surface area,
and absorbency to guest molecules have received boundless
attention for use in SCs. One of the critical issues of the MOFs
is their conductivity. Primarily, MOFs show less conductivity,
which is not beneficial to electrochemical devices. However,
when the MOFs are mixed with conducting materials like
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conductive graphene and polymer, the metal shows high
potential as a leading electrode in SCs devices.161 Zhang and
co-workers established the method of a SDS Zn−Co−S HC
structure and inspected it as an electrode for SCs.164 The
elevated surface area, suitable Zn/Co molar ratio of DS Zn−
Co−S HC, and weight fraction of the active species resulted in
better performance. The improved capacitance is in excess of
1266 F/g at 1 A/g and has a magnificent rate capability for
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hybrid SCs as battery-type electrode materials. The DS Zn−
Co−S maintained a cycling stability of 91% after 10 000 cycles,
and single-shelled Zn−Co−S had a 19% capacitance loss under
a similar environment. Generally, the electrochemical capa-
bility of double-shelled Zn−Co−S was remarkably higher than
reported Zn/Co−sulfide-based electrodes for hybrid super-
capacitors. The tactics which are essential for the advancement
of supercapacitive performance could be compiled as follows:
good dispersion of nanoparticles, existence of a hollow shell
porous framework, which allows it to detain nanoparticles, a
huge channel for smooth movement of electrolyte ions,
addition of N2 (nitrogen) or other compounds for optimum
electrical conductivity, and availability of conductive networks
so electrons can move easily.152 Ultrathin nanosheets of
NiCo−MOFs were also used for a high-performance super-
capacitor.165 The authors prepared NiCo−MOF nanosheets
by an ultrasonication method using NiCl2 and CoCl2 as the
metal salt and terephthalic acid as the organic linker. The
effective molar ratio of Ni to Co ions in the synthesis of the
MOF enhanced the electrochemical properties. The electro-
chemical reversibility and capacitive performance are shown by
the nearly symmetric charge−discharge curves at all current
densities. Figure 9b displays the specific capacitances
computed from the discharge curves. At the same current
density, the NiCo−MOF electrode clearly displays an
optimum specific capacitance of 1202.1 F/g at 1 A/g
compared to the Ni−MOF (840 F/g) and Co−MOF (650.6
F/g) electrodes. These results demonstrate the ultrathin
NiCo−MOF nanosheets’ potential as high-performance super-
capacitor electrode materials.
5.4. MOF Membrane for Wastewater Treatment and
Water Revival. A MOF made by a metal ion and bridging
ligands has been shown to display preferable membrane
separation performance. It was noted that the MOF could
increase the selectivity based on its accurately determined pore
size, while pores could be controlled in a wide series of guest
species shapes and sizes.166 Various types of MOFs are
available, but the necessary condition for MOFs for use in
wastewater treatment and water revival is the stability of MOFs
in water. MOFs to be selected as fillers for membranes depend
on the following factors: (i) the MOFs have higher selectivity
and permeability, (ii) they have uniform and tunable pore
structures, (iii) they have greater affinity, and (iv) they can be
recycled and reused as fillers in some cases. MOF composite
membranes refer to MOFs mixed with polymers as nano- or
microparticles to design MOF composite membranes.
Polymer-based MOFs overcome cooperation linking with the
selectivity and permeability of the polymeric membrane and
also increased the thermal stability and mechanical strength of
the membrane.167,168 MOFs can act as filler TFN membranes
and MMM to construct MOF-based composite membranes for
wastewater treatment and water revival. The ideal MOF
membranes were tested, but the structural defects in the MOF
materials were unavoidable. Hence, how to design a defect to
be an ideal MOF membrane is currently under debate. The
MOF particles’ surface properties, MOF membrane, and MOF
structure limitations have also been studied to be essential
factors. Due to the versatile pore diameter of the MOF
membranes, they have excellent application possibilities in
water treatment. There are MOF membrane applications such
as membrane distillation, membrane filtration, and membrane
pervaporation, which are described below.169
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5.4.1. Membrane Filtration. Membrane filtration is the
standard method for separation that permits molecular scale
filtration. The particular permeability of the membrane pores is
used to separate contamination. Notably, the membrane acts as
wall that allows movement of the solvent, inorganic ions, tiny
molecules, etc., via a membrane and holds macromolecules and
particles (Figure 10a). The MOF membrane can be further
categorized to enhance the efficiency of filtration like UF, MF,
NF, and RO.169
5.4.1.1. Microfiltration. Macromolecules, suspended par-
ticles, and colloids are purified, concentrated, or separated
from solution using this pressure-driven separation techni-
que.170 Microfiltration (MF) retains particles between 0.1 and
1 μm. The MOF composite MF membrane is widely used due
to the membrane’s properties being enhanced by MOFs. Ragab
and co-workers redesigned a ZIF-8-based PTFE double-layer
MF membrane to get a ZIF-8/PTFE membrane for removal of
micropollutants (progesterone) from wastewater.171 The
outcome was that the adsorption capacity was enhanced
about 40% and there was double water permeability (Figure
10b). This was due to the hydrophobic nature of ZIF-8, which
minimizes the friction between the membrane surface and
water; hence, there is an increase in the permeability and also
the formation of a hydrogen bond between the MOFs and
water to enhance the hydrophilicity, thereby increasing the
permeability.
5.4.1.2. Ultrafiltration. In this membrane, filtration forces
such as the concentration or pressure gradients lead to
separation via a semipermeable membrane. Suspended
particles and solutes with a high molecular weight were
trapped, while water and solutes with a low molecular weight
pass through the membrane.172 It has small pore size ranging
from 0.001 to 0.1 mm and requires a high driving force for
filtration. Ultrafiltration (UF) membranes have been widely
applied and studied in industry due to the magnificent
performance in eliminating suspended nanoparticles, macro-
molecules, bacteria, etc.173 Nowadays, MOFs are mixed with
various materials like silica, graphene oxide, titania, etc., instead
of existing materials to switch the compatible properties before
compounding with polymeric ultrafiltration membranes.
Attention can be moved to the eco-friendly MOF−base
composite membrane with high permeability and stability with
antifouling characteristics, making it even more eco-friendly in
manufacture application.174 UiO-66 was functionalized by
graphene oxide to fabricate UiO-66@GO; then, a UIO-66@
GO/PES composite membrane was synthesized by PES.175
The outcome indicated that 3.0 wt % of UiO-66 upgraded the
rejection rate, flux, hydrophilicity, and antifouling property, as
shown in Figure 10c. The CA/MOF@GO MOFs composite
membrane was prepared using cellulose acetate (CA) as the
base membrane, while MOF@GO was used as a filler.176 The
benefits of MOF@GO fillers mixed with hydrophilic GO and
MOFs porous structures enhance the preferable membrane
properties. The results exhibited the highest water flux of
183.51 L/m2 h of CA/MOF@GO and better antifouling
performance. Ultrafiltration is one of the most frequently
methods for water decontamination and is also used in reverse
osmosis pretreatment.
5.4.1.3. Nanofiltration. Nanofiltration (NF) is a low
pressure-driven membrane method which lies among UF and
RO as far as its capacity to reject ionic or molecular species.
The nanofilter may have a larger free space, small pores, or
nanovoids available for transport.177 NF permits inorganic salts
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and solvent to go through the membrane to reach the
separation. Due to its efficacy in environmental applications,
the NF method is extensively used in water treatment. Golpour
and co-workers prepared PA-MOF/PPSU-GO, a novel MOF
membrane for nanofiltration for treatment of wastewater
containing KHI.178 The outcome was that the as-prepared
MOF composite membrane enhanced by 50% the hydro-
philicity and antifouling properties of permeation flux, which is
greater than the original polymeric membrane, and rejection
persisted similarly at more than 96% (Figure 10d). Yuan et al.
synthesized a novel ZIF-300 membrane to remove heavy metal
ions from wastewater.179 This ZIF-300 membrane has a stable
and high water permeability of 39.2 L/m2 h bar with a 99.21%
rejection rate. Therefore, pure ZIF-300 membranes will be
used for wastewater heavy metal ion nanofiltration.
5.4.1.4. Reverse Osmosis and Forward Osmosis. Reverse
osmosis (RO) happens when a solution is pressed against a
solvent-selective membrane and the applied pressure is greater
than the difference in the osmotic pressure across the
membrane.180 It is a preferable membrane-based method for
water desalination. Conversely, forward osmosis (FO) happens
when the osmotic pressure gradient is positive between the
feed and the draw solution and the solution is at a similar
hydrostatic pressure.169 Liu and co-workers produced a pure-
phase Zr−MOF (UiO-66) polycrystalline membrane on an
alumina hollow fiber for desalination via a one-step
solvothermal synthesis.181 To assess the desalination efficacy
of the membranes as feeds, five different aqueous brine
solutions with 0.20 wt % concentrations of NaCl, KCl, MgCl2,
CaCl2, and AlCl3 were used. The results showed that the
membranes had exceptional multivalent ion repulsion for Mg2+
(98.0%), Ca2+ (86.3%), and Al3+ (99.3%) as well as fine
permeability. Furthermore, Hee and co-workers synthesized a
RO MOF composite membrane by combining a PSF
membrane with HKUST-1[Cu3(BCT2)] MOF.182 The results
showed a 33% increase in water flux and a small increase in salt
rejection to 96% (Figure 10e). Recently, CuBDC-NS, a 2D
MOF nanomaterial, was discovered as a filler in PA to design a
suitable TFN membrane.183 The results showed a 50%
increase in water flux through the TFN membrane and a
50% reduction in specific reverse solute flux using 1.0 M NaCl
for AL-FS mode (Figure 10f). A novel area of interest in MOF
repurposing of RO and FO membranes is the control of the
MOF size to alter the performance of the membrane and
increase the filter efficiency.
5.4.2. Membrane Distillation. Membrane distillation (MD)
is an effective separation technique that can reduce water
energy stress in an environmentally friendly manner. To drive
desalination, separate nonvolatile pollutants, or extract other
components, MD requires low-grade thermal energy. In MD,
an aqueous solution’s vapor travels through a hydrophobic
membrane and then condenses on the other side of the
membrane to produce a high-quality distillate.184 The driving
force behind the separation is the vapor pressure on the two
sides of hydrophobic porous membrane.169 DCMD, AGMD,
SGMD, and VMD are four forms of MD currently
available.185,186 Thermostability, hydrophobicity, improved
thermal conductivity on the feed side, and low mass transfer
resistance are all characteristics of MD membranes.187 In order
to create new MOF composite membranes for desalination,
Zuo and co-workers discovered an alumina-based MOF
membrane.188 Because of the MOF functionalization, hydro-
phobicity was increased. Fan and co-workers developed a
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Review
superhydrophobic poly(vinylidene fluoride) nanofiber-based
membrane with 5 wt % of MOF-loaded nanofiber for
desalination.189 The outcome showed that the water contact
angle increased to 138.06 ± 2.18°, the water vapor flux
increased, and the was a 99.99% NaCl rejection rate (Figure
11). MD is utilized in the food industry and heavy metal
Figure 11. PVDF and PV-1 flux and permeate conductivity in
DCMD. Reprinted with permission from ref 189. Copyright 2018
American Chemical Society.
removal in addition to desalination. The use of a photo-
thermally enhanced material for membrane distillation could
increase the energy efficiency of MD. The chemical stability,
hydrophobicity, and thermal characteristics of the membrane
could be improved with the addition of a MOF.
5.4.3. Membrane Pervaporation. Pervaporation (PV) uses
a membrane-selective barrier between the feed liquid phase
and the permeate vapor phase in order to separate the two
phases. It enables the vaporization of the desired compo-
nent(s) of the liquid supply to pass through it. On the basis of
a difference in how quickly each component moves across the
membrane, components can be separated.190 This is due to the
fact that the driving force for the vapor pressure in PV is
different from that for membrane distillation. Also, PV is less
energy consuming and more energy effective than MD because
of the feed solution and permeate vapor. Typically, the best
permeate flux and separation factor are provided by the PV
membrane. Organic solvents in water are primarily removed
and recycled using a PV membrane. As the PV membrane can
be either organophilic or hydrophilic depending on the
application, it is also employed for recovery of organic
solvents.191 A superhydrophobic MAF-6 into PDMS was
reported to design MMM for the recovery of ethanol.192 MAF-
6’s hydrophilicity and high porosity increased the membrane’s
permeability, selectivity, and stability. When MAF-6 was
loaded to MMM, the hydrophobicity reached 15 wt %.
According to experimental findings, the MMM membrane
shows remarkable hydrophobicity when MAF-6 loading was 15
wt %, resulting in the highest flow of 1200 g/m2 h and a
separation factor of 14.9. For the purpose of developing an
MMM for the recovery of 1-butanol, they also discovered a
ZIF-8 particle that was reconstructed through silanization into
PDMS.193 The results revealed that these particles increased
the 1-butanol flow 85% and had a 34% separation factor
(Figure 12a). Since recovering organic solvents is the main use
of pervaporation, the stability, selectivity, hydrophobicity, and
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Figure 12. (a) Comparison of pure PDMS membrane and MMMs combined with unmodified and modified ZIF-8 particles in 1.5 wt % 1-butanol
at 55 °C for PV. Reprinted with permission from ref 193. Copyright 2019 Elsevier. (b) Comparison between the capacity of control CA and the
MOF@CA toward methylene blue cationic dye, methyl orange anionic dye, and dichromate ions. Reprinted with permission from ref 194.
Copyright 2020 American Chemical Society.

permeability of the PV membrane are crucial. Moreover,
MOF-based MMM was also used for water decontamination.
Worood and co-workers prepared a MMM that contained
UiO-66-NH2 MOFs as the adsorbent and CA as the polymeric
matrix to prepare MOF@CA MMM for the removal of water
contamination.194 First, they prepared UiO-66-NH2 by using
ZrCl2 as a metal salt and 2-aminoterephthalic acid as an
organic linker. Then, freshly prepared UiO-66-NH2 crystals
were added to the cellulose acetate solution via stirring for 3 h.
The solution was transferred into a glass Petri dish and dried
overnight at room temperature. The synthesized MOF@CA
MMM showed excellent performance in the removal of organic
dye (methyl orange and methylene blue) and dichromate ions
in comparison to the control polymer cellulose acetate
membrane (Figure 12b). Hence, MOF-based membranes
proved the approachability of the MOF nanocage immobilized
within the MMM. The effective application of such a strategy
to develop novel membrane materials for wastewater treatment
applications should be based on the optimum hybridization of
the chosen polymer matrix and the MOF filler to address the
required conditions in a given context.
Other applications include catalytic application, which have
been extensively employed for various transformations such as
Friedel−Crafts reactions,195,196 condensation reactions,197,198
oxidations,199,200 coupling reactions,201,202 carbon dioxide
44523
fixation,203 cyano silylation,204,205 etc. More could be learned
about the potential uses of MOFs in sustainable green catalysis,
including biocatalysis, solvent-free catalysis, designing catalysts
for reactions in environmentally friendly solvents, and
enhancing the recyclability of catalysts. The application of
sensing has recently drawn some study interest. For sensing
purposes, carbon nanoparticles and metal oxide nanocompo-
sites are utilized.
6. CONCLUSION AND FUTURE PERSPECTIVES
This report has covered the classification, nomenclature,
synthesis methods, influencing factors, potential applications,
as well as the biomedical applications of the metal−organic
framework. It has explained how MOFs can be classified and
synthesized with interesting characterization. Although the
conventional hydro/solvothermal synthesis method was
adequately used in MOF synthesis, unconventional and new
methods like electrochemical, mechanochemical, sonochem-
ical, microwave-assisted, etc., methods are just materializing in
this extent.206 These are crystalline porous materials in which
the metal is fixed in place to fabricate a porous and rigid
geometry and uses various bridging ligands.61 Alternative
methods lead to the MOFs having various properties. Potential
applications of MOFs have also been discussed within the
energy industry, such as next-generation rechargeable batteries
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and novel supercapacitors. Due to their well-regulated advantages and enhances the performance of the resulting
morphology with a flexible structure, a relatively high surface composites with regard to membrane separation, energy, and
area, accessible metal sites, and a huge pore volume, MOFs catalysis. We assume there will be more logical and large-scale
and their composites are interesting and potential electrode methods of the controlled synthesis of nanosized MOFs, which
materials for energy storage devices. However, the stability of will help to serve for improved performance, with the
the MOF materials in air is one of the drawbacks of energy continuous efforts of scientists and the development of the
storage devices which restricts good electrochemical perform- nano-MOFs field. We anticipate hearing about a lot of
ance. Doping heteroatoms or introducing metal oxides will fascinating nano-MOF-related results in the near future.
further enhance the electrochemical performance of the MOFs.
In addition, it has been highlighted how the superior
compatibility and incredibly adaptable pore structure of
■ AUTHOR INFORMATION
Corresponding Author
MOF membranes have led to its employment in a variety of Suresh Kumar Kailasa − Department of Chemistry, Sardar
applications (including wastewater treatment and water Vallabhbhai National Institute of Technology, Surat, Gujarat
regeneration). The water stability of the MOF membrane 395007, India; orcid.org/0000-0003-4058-0145;
limits this application in terms of how to maintain the long- Phone: +91-9033369827; Email: sureshkumarchem@
term stability of the membrane in alkaline and acidic media, gmail.com, skk@chem.svnit.ac.in
complexation of MOFs with organic solvents, temperature
variations, and commercialization of MOFs in eco-friendly Authors
ways. Hence, there is a need to develop water-stable MOF Vadia Foziya Yusuf − Department of Chemistry, Sardar
membranes with a facile method. MOFs are widely applied in Vallabhbhai National Institute of Technology, Surat,
biomedical applications, specifically in drug delivery systems. Gujarat 395007, India
Nevertheless, the solubility and toxicity of the chosen metal Naved I. Malek − Department of Chemistry, Sardar
salts and organic linkers for synthesized MOFs as well as the Vallabhbhai National Institute of Technology, Surat,
problems with biocompatibility are key issues for drug delivery Gujarat 395007, India; orcid.org/0000-0002-2164-
applications. Also, pore encapsulation and surface adsorption 5268
are also the main factors for strong interaction which limits the Complete contact information is available at:
application. Thus, it is necessary to design MOF−drug https://pubs.acs.org/10.1021/acsomega.2c05310
conjugates with improved biostability, biocompatibility, and
therapeutic efficiency. In addition, the pressure, temperature Notes
and composition play chief roles in the H2 adsorption in The authors declare no competing financial interest.
MOFs. The adsorption capacity of H2 has been observed to be
very low at ambient temperature and pressure to date. Thus,
improving the adsoption capacity of MOFs at high pressure
with a stable structure is still a challenge. As there is a large
■ ACKNOWLEDGMENTS
Authors thank the Director, Sardar Vallabhbhai National
amount of flexibility in tailoring the structural framework and Institute of Technology, Surat for providing necessary facilities
functionalization, it is likely that MOFs will assume a for this work.
substantially more significant role in the future to achieve an
elevated level of application
Research in the field of MOFs is expanding quickly in both
■
2D
ABBREVIATIONS
two dimensional
academia and industry. MOFs are a potential new type of 3D three dimensional
material that has incredible adaptability and the ability to 5-FU 5-fluorouracil
address a number of 21st century global concerns. Most of the AGMD air gap membrane distillation
effort in the future will be devoted to developing novel AlCl3 aluminum chloride
materials through green synthesis, conducting related AL-FS active layer-oriented feed solution
fundamental research to increase the structural variety of APIs active pharmaceutical ingredients
MOFs, and using those materials in a variety of potential AS2O3 arsenic trioxide
applications. Metal−organic frameworks (nano-MOFs) at the BDC 1,4-dicarboxybenzene
nanoscale have garnered a lot of attention recently due to the bpy 4,4′-bipyridine
discovery of numerous features like structural diversity, high BTC 1,3,5-benzenetricarboxylate
surface area, and tailorability. In addition, nano-MOFs offer btze 1,2-bis(tetrazole-1-yl)ethane
some special benefits like rapid adsorption/desorption kinetics, CA cellulose acetate
physiological stability, and access to the interior active parts.207 CaCl2 calcium chloride
Moreover, nano-MOFs have been extensively studied in CAF caffeine
biomedicine due to their small sizes and remarkable Co3O4 tricobalt tetroxide
biocompatibility. A number of functional nano-MOFs have CoCl2 cobalt chloride
been developed for therapeutic activities, such as porphyrin CuBDC-NS Cu−1,4-benzene-dicarboxylate nanosheet
and its derivative-based nano-MOFs which are competitive in CVD chemical vapor deposition
various biomedical therapies.208,209 Hence, the development of DCMD direct contact membrane distillation
nano-MOF treatments with high biological safety would be the DDS drug delivery system
focus of a futuristic approach to the synthesis of nano-MOFs, DEF diethylformamide
which is absolutely necessary. In addition, these materials offer DMA dimethylacetamide
excellent adaptability/compatibility with other components, DMF dimethylformamide
which considerably helps the integration of their individual DMSO dimethyl sulfoxide
44524 https://doi.org/10.1021/acsomega.2c05310
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DNA deoxyribonucleic acid TBATFB tetrabutylammonium tetrafluoroborate

DOX doxorubicin TFN thin-film nanocomposites
DS double shelled TGA thermogravimetric analysis
EDLCs electric double-layer capacitors UCNP upconversion nanoparticle
eim 2-ethylimidazole UF ultrafiltration
EtOH ethanol UiO University of Oslo
Fe2O3 ferric oxide VMD vacuum membrane distillation
Fe3O4 iron oxide ZIFs zeolitic imidazolate frameworks
FO forward osmosis
GO graphene oxide
H2BDC
H2IPA
1,4-benzene dicarboxylic acid
isophthalic acid
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