Energy, Drug, waste water treatment MOF review

http://pubs.acs.
org/journal/acsodf Review
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
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
44507 ACS Omega 2022, 7, 44507−44531
ACS Omega http://pubs.acs.org/journal/acsodf Review
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
Figure 1. Formation of MOF structure by formation of chemical multitopic ligands) responds to the metal ion by means of
bonds between the metal ions as nodes and the organic molecule as a more than one labile or vacant position. The ultimate
linker. framework is reigned over via both the metal ion and the
primary building unit (PBU).2
elements are metal ions or clusters called secondary building The metal ion and bridging ligands might provide diverse
units (SBUs).8 The geometry of the MOFs is considered outcomes in an assortment of MOFs, customized for typical
Figure 2. Organic molecules as linkers used for the preparation of MOFs.
44508 https://doi.org/10.1021/acsomega.2c05310
ACS Omega 2022, 7, 44507−44531
Figure 3. MOFs with various metal nodes and organic linkers.
applications.7 The enormous spaces of MOFs may bring about 2. CLASSIFICATION AND NOMENCLATURE OF
the improvement of interpenetrating structures. In this way, it METAL−ORGANIC FRAMEWORKS
is vital to prevent interpenetration by sensibly selecting the
2.1. Classification of MOFs. When combined with specific
PBU. The pore’s size is ensured, and the arrangement of the materials, like metal oxides, quantum dots, carbon materials,
spatial cavity can be managed by carefully selecting the metal molecules, polyoxometalates, polymers, and enzymes, one can
center and organic linkers and via varying the synthesis prepare MOF nanocomposites that have functional diversity.
conditions. MOFs are prepared by several approaches such as Depending on their component unit, MOFs could be divided
solvothermal, microwave-assisted, ultrasonication, mechano- into a variety of groupings.19
chemical, electrochemical, ionothermal, and sonochemical 2.1.1. Isoreticular MOFs. Isoreticular MOFs are synthesized
processing. The huge porosity permits their utilization in by [Zn4O]6+ SBU and a series of aromatic carboxylates. They
separation and adsorption of gaseous molecules, micro- are octahedral microporous crystalline materials. In recent
electronics, catalysis, optics, bioreactors, drug delivery, sensing years, for the advancement of sensors, IRMOF-3 has been used
applications, and so on. A fascinating and remarkable abundantly. Zhu and co-workers synthesized nanosheets of
development in this field is MOFs combined with functional IRMOF-3 with magnificent sensitivity and selectivity toward
nanoparticles, resulting in novel nanocomposite materials with recognition of 2,4,6-trinitrophenol in wastewater.20,21
exceptional characteristics and applications. Nanoparticle 2.1.2. Zeolitic Imidazolate Frameworks (ZIFs). Zeolitic
composite MOFs have various chemical and structural imidazolate frameworks are synthesized using various elements
diversities, excessive loading capacity, and high decompos- that have valence electrons and imidazole derivatives. They are
ability; thus, they are beneficial to traditional nanomedicines.2 zeolite topological structured materials. ZIFs comprise ZIF-8,
In addition, MOFs and their composite materials have been ZIF-90, ZIF-L, ZIF-71, ZIF-67, ZIF-7, etc.19 The ZIF-8
used as electrocatalysts for the ORR,9−11 carbon dioxide material is discussed beyond the diverse ZIF materials due to
reduction,12 the HER, and the OER.13,14 MOFs have so far its dominant performance, such as the sensitivity of the acid,
attracted a lot of interest in several research fields, both with excessive surface area, lower cytotoxicity, immense pore size,
the aim of developing and synthesizing novel materials as well etc.22 Pan and co-workers designed a ZIF-8 MOF for detection
as for a wide range of applications. In recent years, numerous of the HIV-1 DNA.23 ZIFs have a huge pore size and superior
reviews of electrically conductive MOFs,15 2D MOFs,16 the chemical and thermal stability that is used as a network to
history of activation and porosity,17 clean energy applica- develop novel MOF composites.24,25
tions,18 and so on have been published. In this article, we 2.1.3. Porous Coordination Networks (PCNs). Porous
provide a history of MOFs, their classification and the coordination networks are stereo-octahedron materials, and
nomenclature of MOFs (i.e., how to classify newly synthesized they have a hole−cage−hole topology with a 3D structure.
MOFs from a historical point of view), synthetic approaches Some of the PCNs are PCN-333, PCN-224, PCN-222, and
for MOFs, and various influencing factors for the synthesis of PCN-57.19 One of the PCN MOFs, PCN-222 MOF, is
MOFs. Moreover, their potential applications in various fields extensively applied in sensors. Ling et al. synthesized a
such as gas storage, drug delivery, electrochemical energy susceptible electrochemical sensor to detect DNA by using
conservation, and removal of water contaminants are PCN-222.26
discussed. In addition, the advantages and disadvantages of 2.1.4. Materials Institute Lavoisier (MIL) MOFs. Materials
the synthesis approach for creating MOFs are emphasized. The Institute Lavoisier MOFs are synthesized using various
review comes to a close by outlining several crucial future elements that have valence electrons and an organic compound
directions for the creation of nano-MOFs and their containing two carboxylic functional groups. The pore size
applications. 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 the absence of any metal salts, the formation of any corrosive
nanocrystals. Microwaves with frequencies between 300 and anions like nitrate and by-products are avoided, making the
300 000 MHz are a sort of electromagnetic radiation.63 deposition environment friendly. The key component of this
Microwave-assisted MOF synthesis is mainly focused on technique for MOF synthesis is that metal ions are added
rapid crystallization and formation of nanoscale products to through an electrochemical procedure rather than through a
enhance product purity for the particular synthesis of solution of the corresponding metal salt or by production of
polymorphs.65 these ions following a metal’s reaction with acid.65 The
3.2. Electrochemical Method. The electrochemical electrochemical method of MOFs uses electrons as a source of
method is used for the rational construction of a vast number metal ions that are passed through a reaction mixture, which
of MOFs. HKUST-1 was first synthesized by BASF in 2005 contains dissolved organic linker molecules and an electrolyte
through the electrochemical method.69 Their primary aim was via anodic dissolution as the metal source instead of metal
to isolate anions like chloride, perchlorate or nitrate salts.62 The electrode is placed in a solution that contains PBU
throughout the synthesis procedure, thereby avoiding the and frequently contains an electrolyte. By giving a suitable
formation of corrosive anions (nitrate and chloride), which can voltage, the metal is dissolved and the metal particles essential
be considered that electrochemical method is a green for the development of MOFs are present exterior to the
chemistry approach for MOFs preparation bother to extensive electrode’s surface. The metal ions instantly respond with the
construction procedures. Since the synthesis is carried out in 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 aids the reaction. In addition, to acquire a large crystal with a
solvent, the metal deposition on the cathode escapes; however, high internal surface area, slow crystallization from a solution is
H2 is produced. The electrochemical route is too feasible to required.
run a consistent procedure to acquire a higher solid content 3.4. Mechanochemical Method. Mechanochemistry
than the ordinary batch reaction.70 concentrates on responses between solids usually for the
3.3. Solvothermal Method. The solvothermal method most part started just using mechanical energy. A combination
has been widely used for the preparation of MOFs. This of a metal salt and an organic ligand is ground in a ball mill or
technique is employed due to its simplicity, convenience of with a mortar and pestle in the absence of solvent; then, the
usage, crystallinity, and high yield. In this approach, metal salts ground mixture is heated mildly to evaporate other volatile
and organic ligands are stirred in protic or aprotic organic compounds and H2O, which formed as a byproduct in the
solvents which contain the formamide functionality.73 Aprotic reaction mixture.61 The mechanochemical approach for the
solvents include DEF, DMF, NMP, DMSO, DMA, acetonitrile, preparation of MOFs is an easier method than the other
and toluene. Protic solvents are methanol, ethanol, and mixed methods (Scheme 4). In mechanochemical synthesis, chemical
solvents. To keep away from the issues associated with the transformation takes place through mechanical breaking of
distinct solubility of the initial components, mixtures of intramolecular bonds.79 This reaction exists at room temper-
solvents can be used. If water is used as a solvent in MOF ature, and organic solvents can be avoided. The first MOF
synthesis, it is referred as the hydrothermal method.70 This synthesis through this approach was reported in 2006.80
mixture is poured into the closed vessel at elevated pressure Currently, this method is used on a large scale for the
and temperature for several hours or a day. Glass vials are used preparation of various kinds of MOFs.
at low temperature, and a Teflon-lined stainless-steel autoclave 3.5. Sonochemical Method. Recently, the sonochemical
is used for high temperature (>400 K) in the reaction (Scheme method has been used for rapid synthesis of MOFs as it
3). Then, the closed vessel is heated at a temperature greater decreases the time for crystallization through ultraradiation. In
than the aprotic or protic solvent’s boiling point to bring about this method, a cyclic mechanical vibration (from 20 kHz to 10
higher pressure.73 The chief parameter of this reaction mixture MHz) is used for the synthesis of the MOF.83 In a horn-shaped
is the temperature, and there are two temperature ranges, i.e., Pyrex reactor with a sonicator bar and a variable power output,
the reaction taking place in a closed vessel above the solvent’s a mixture of the metal salt and organic linker is added without
boiling point under autogenous pressure referred to as a the use of external cooling62 (Scheme 5). The main factor for
solvothermal reaction, and a nonsolvothermal reaction the cavitation’s impact on a liquid is ultrasonic. Cavitation is
happens below or at the boiling point of the solvent under the name for the development and collapse of bubbles created
ambient pressure.74 Due to the high pressure, the solvent is in a solution after sonication. It produces very fine crystallites
heated above its boiling point and the salt will melt, which then 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 or more solution in the inner nozzle at a definite speed (feed
time for the synthesis of MOFs.84 Table 2 provides examples rate). The outer nozzle compresses air or nitrogen at another
of MOFs prepared by various synthetic routes (microwave, constant speed (discharging rate). Then, each atomized
electrochemical, solvothermal, hydrothermal, mechanochem- droplet is heated at a specific temperature through a gas and
ical, and sonochemical methods). starts to evaporate. Solvent evaporation increases the
Apart from these, other methods such as the diffusion precursor’s concentration at the surface until large particles
method, spray-drying synthesis, ionothermal synthesis, and of MOFs begin to form.88 The diffusion method is divided into
chemical vapor deposition have been used for the synthesis of two phases: (i) gas-phase and (ii) liquid/gel-phase diffusion. In
MOFs.87 In the spray-drying method, atomization of a solution this method, diffusion of one of the reagents has a controlled
consisting of MOF precursors into a microdroplet spray is reaction rate. Gas-phase diffusion consists of an organic ligand
performed using a two-liquid nozzle. The process injects one 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 types based on their coordinating groups, including carboxylic
dissolved in immiscible solvents. In the gel-phase diffusion acid-based linkers, nitrogen-containing heterocyclic, phosphor-
method, the metal ion and organic ligand are dispersed in a gel yl, and sulfonyl linkers, cyano linkers, etc. Carboxylic acid-
substance and crystallization begins. This method is often based linkers are among the different organic linkers, and they
performed under moderate conditions but is a time-consuming are frequently chosen as multifunctional organic linkers as they
reaction.70 In ionothermal synthesis, an ionic liquid acts as have many coordination nodes to act as H-bond acceptors and
both the solvent and the structure-directing agent. Here, an donors to metal ions, which allow for a variety of structural
ionic liquid is used as a charge balance group, structural topologies to assemble MOF structures.102 Heterocyclic linkers
template, or reaction medium. Thus, the ionothermal method that contain an N atom have distinct coordination patterns,
provides a pure ionic environment. The physicochemical which increase the target compound’s capacity to be controlled
characteristics of MOFs can be measured by altering the structurally.103 For the fabrication of novel MOF structures,
composition of the ionic liquid. Some merits of this method mixed linkers are another option for creating new MOFs that
are a lower melting point, good thermal stability, and varied have novel structures.104 One of the typical methods to
liquid range.89 CVD is also known as a solvent-free method produce higher dimensional networks is to extend the metal
which is used to make crystalline materials in the semi- carboxylate complexes with a second bridging ligand. More-
conductor industry. This method has two steps: in the first over, the structure of MOFs may be significantly impacted by
step, atomic layer deposition via vaporized metal and oxygen the positional the isomerism of ligands with the same
or water precursors forms a metal oxide thin film, and in the coordination groups but located in different places. For
second step, vaporized ligand sources are introduced to instance, the aromatic dicarboxylic acids H2IPA and H2TPA
transform the metal oxide film and crystals begins to form.90 both have the tendency to bind and are engaged in controlling
However, each MOF synthesis has some merits and demerits. the MOFs’ structural assembly.105 The linker L combined with
The solvothermal method is a one-step synthetic approach that these two linkers to form {[Zn(L)(IPA)]}n and {[Zn(L)-
gives single crystallinity at a moderate temperature.91 On the (TPA)]·DMF} n complexes with the Zn 2+ metal ion,
other hand, this method takes a long period of time, requires respectively, via the solvothermal method. The H2IPA linker
more solvents, and produces acids as byproducts.92 In the combines with L and forms 1D chains of {[Zn(L)(IPA)]}n,
microwave-assisted method, MOFs are generated with a and the H2IPA is replaced by H2TPA, which forms a 3D
uniform morphology by means of rapid crystallization in less structure of {[Zn(L)(TPA)]·DMF}n. The selection of the
time and also give a high yield in particular phase purity. It is metal salt plays a significant role in the synthesis of MOF
challenging to change the reaction conditions by controlling structures. Salts utilized as metal sources can be divided into
the irradiation power. Reproducibility is eventually hindered by two categories: inorganic acid salts and organic acid salts. Most
the inability of the many instruments to simulate the same of the inorganic salts used are carbonates, sulfates, and nitrates,
variables; as a result, the temperature and reaction time are also and the organic salts are mostly acetates and their
limitations of the microwave-assisted method.93,94 The electro- derivatives.106 For instance, [Cu3(btc)2] was prepared by
chemical method generates more solids compared to the batch using two different metal salts Cu(OAc)2 and Cu(NO3)2 and
process and can be applied as an industrial approach to form H3BTC as the organic linker. The result revealed that
MOFs.95 It has been noted that the MOFs produced by the Cu(OAc)2 was favorable for the preparation of [Cu3(btc)2]
electrochemical method are of lower quality since the linker with a high surface area.107 In addition, by adjusting the metal
molecules and/or conducting salt were included in the pores ions and the coordination modes of the organic ligands, it is
during crystallization.96 There are numerous reasons to be possible to predict the topology of the MOFs; also, the stability
interested in mechanically activated MOF synthesis. Environ- of the MOF is generally improved by the presence of
mental concerns are thus one of the important points. numerous metal ions that are connected by various
Reactions can be performed with solvent-free conditions at coordinating ligands. The metal ions serve as the MOF’s
room temperature, which is particularly helpful in situations by construction node and have a direct impact on the structures
avoiding organic solvents. It is possible to produce MOFs with of MOFs through their coordination geometry. In the synthesis
few components and to achieve quantitative yields in a short of MOFs, the concentration of the precursors (molar ratio) is
amount of time.97 Moisture is the main challenge in the also a significant factor. The topological patterns of MOFs are
synthesis of MOFs via the mechanochemical method. Single mostly dependent on the ratio of metal ions and organic
crystallization and a lower pore size are limitations of the linkers.101 Liu and co-workers explored the effect of the metal
mechanochemical method.98 Sonochemical synthesis in MOF to linker molar ratio on the synthesized MOF structure by
chemistry is developing a technique that is rapid, energy using CoCl2 and btze.108 The result showed that the initial
efficient, eco-friendly, simple to use, and operable at room materials with a molar ratio of Co(II)/btze of 1:1 or 1:1.5 form
temperature.99 Crystal decomposition happens during the long 2D [Co(btze)2(SCN)2]n MOFs. When they used a molar ratio
reaction time of the synthesis of the MOFs.100 Currently, of 1:2 or more btze linker, a 3D [Co(btze)2(SCN)2]n MOF
particular attention is given to the synthesis of MOFs to step structure resulted. Various coordination modes can be adopted
up the crystallization of MOFs by rapid reactions. Merits and by organic linkers at different pH ranges.109 Moreover, as the
demerits of various synthetic approaches for the preparation of pH value rises, the linker deprotonates to a greater extent. For
MOFs are described in Figure 4. example, by raising the pH, the Al3+ ion coordinates with 4, 6,
and 8 −COOH groups, yielding MIL-121 (at pH 1.4), MIL-
4. INFLUENCING FACTORS FOR SYNTHESIS OF MOFS 118 (at pH 2), and MIL-120 (at pH 12.2), respectively.110
The synthesis of MOFs has been affected by several exterior Spectroscopic data revealed that MOFs are formed with an
factors, such as the selection of organic ligands, metal ion salts, interpenetrated network at higher pH and were uninterpene-
molar ratio, pH, solvents, and temperature of the reaction trated at a lower pH.111 The color of the MOF compounds
media.101 Organic ligands can be categorized into a number of 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 hydrothermal approach at higher temperature and at room
complexes, viz. [Co2(L′)(HBTC)2·(μ2-H2O)·(H2O)2]·3H2O temperature, illustrating that a Ho−succinate MOF prepared
(1), [Co3(L′)2·(BTC)2]·4H2O (2), and [Co2(L′)·(BTC)·(μ2- via the hydrothermal approach is more thermally stable than a
OH)·(H2O)2] ·2H2O (3), which different structures and Ho−succinate MOF prepared at room temperature.118
colors upon varying the pH.112 These three MOFs also showed
different adsorption capabilities. It is also known that materials 5. APPLICATION OF MOFS
of higher dimensions are formed at higher pH.113 In MOFs, there are three properties acting simultaneously,
The solvent plays a significant part in the synthesis of MOFs namely, the crystalline nature, porosity, and presence of strong
and also in morphology determination of the MOFs. Solvents metal−ligand interaction. A rare combination of these
are coordinated through metal ions as a structure-directing properties makes MOFs an exceptional class of materials.
agent. In view of this, solvents with a polar nature and higher The high surface area, small density, structural flexibility, and
boiling points are widely used in MOF synthesis. Generally, tunable pore functionality of MOFs makes them useful in a
solvents like DEF, DMF, DMSO, DMA, acetone, alcohol, broad range of intending applications, such as in gas storage
acetonitrile, etc., are used.114 The MOF preparation process and delivery, drug delivery, rechargeable batteries, super-
was affected by the reaction medium due to the solubility, capacitors, separation membranes, catalysis, sensing, etc.119
solvent polarity, and protolysis behavior of the organic ligand. 5.1. Gas Storage and Delivery. Due to the unique
The different solvents in the same reaction conditions provide structure of MOFs, the key application is gas storage because
different morphologies.61 Banerjee and co-workers reported of their large surface area and absence of dead volume.120 This
MOFs containing magnesium and PDC having various crystal outcome could be noticeable and relies on the pressure,
structures prepared under the same conditions using different temperature, and type of gas used. The MOF material also
solvents115 (DMF, H2O, EtOH, and MeOH) (Figure 5). They plays an important role for this application. Energy-oriented
found that the MOF network’s dimensionality is determined smart applications of MOFs are hydrogen and methane
by the solvent’s capacity to coordinate with the metal. Among storage, carbon dioxide capture, and nitrogen adsorption.121
them, H2O has the highest attraction toward Mg, whereas Molecular hydrogen has more energy than any fuel. The
other solvent mixtures (EtOH:H2O and DMF:MeOH) did not storage and movement of hydrogen gas needs a large amount
coordinate with the metal centers, signifying that the use of of energy compression and liquefaction processes due to the
water as a solvent greatly influenced formation of covalent very low energy density. MOFs draw attention as a result of
bonds with the metal ions. their high surface area, surface to volume ratios, and chemically
The temperature is another critical factor which affects the tunable structures.122 A gas cylinder with a MOF material
characteristics of the synthesized MOFs. Due to the reactant’s could store more hydrogen at a specified pressure in
good solubility and the production of large crystals with high comparison to an empty gas cylinder because a molecule of
superiority, the material exhibits a high crystallization nature at hydrogen adsorbs on the MOF surface.
high temperatures. The temperature of the reaction mixture is As MOFs have no dead volume, there is no loss of storage
affected by the nucleation and crystal growth rates. On varying capacity as an outcome of space blocking by an inaccessible
the reaction temperature, the morphology of the MOF is volume. When the hydrogen is in the gaseous state, MOFs
significantly changed, which allows one to use them for provide optimum benefits of storage capacity, which is
different applications.61,116 To support this, monoclinic and restricted in the liquid state.123 The magnitude of gas that
triclinic morphological Tm−succinate MOFs have been can be adsorbed to the MOF surface relies on the pressure and
successfully synthesized at diverse temperatures using the temperature of the gas. Typically, the adsorption rises when
same empirical formula.117 Bernini and co-workers investigated the temperature decreases and the pressure increases
the thermal stability of Ho−succinate MOFs prepared via the (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 Figure 6. Releasing study of IBU from MIL-53(Cr) and MIL-53(Fe).
hydrogen (7.5 wt % at 77 K up to 40 bar). The two main Reproduced with permission from ref 135. Copyright 2008 American
schemes directing the MOF’s design for hydrogen storage are Chemical Society.
(i) to expand the theoretical storage capability of the MOF
materials and (ii) to carry out working situations nearer to the lation), and acting as an active molecule in a linker process.
surrounding pressure and temperature.126 Typically, the ex situ encapsulation method is too complicated
5.2. Biomedical Applications. In the key area of health and time consuming, as stirring the active MOFs and drug for a
there are many therapeutic disadvantages of APIs, i.e., few days is essential while loading it. However, due to its
unfavorable solubility and stability, less bioaccessibility, short- reliable loading rate, it is still a frequently used method. The
term half-life, and restricted bypassing of biological barriers; one-step encapsulation process has been used for few
because of these reasons, their therapeutic uses are primarily thermostable drugs and certain MOFs because of the deficient
finite. In drug delivery, promotion of an effective drug delivery heat stability of the drug and in high concentration drug
system is one of the dominant areas of research which ensures solution it is difficult to synthesize MOFs.128 Liedana and co-
a favorable result by using safe carrier materials.128 To date, workers discovered two methods for encapsulating caffeine
numerous transit materials have been accounted for and into ZIF-8.136 Here, ZIF-8 was prepared from Zn(NO3)2 ·
structured in various forms, such as carbon dots,129 nano- 6H2O and 2-methylimidazole and the CAF@ZIF-8 IN was
emulsions,130 hydrogels,131 micelles,132 liposomes133 etc. Yet, a prepared via the one-step encapsulation method. The caffeine
greater number of transit materials frequently have low drug was encapsulated inside the pore of ZIF-8. According to TGA
loading capacities, intolerable toxicity, unbound release, and an (Figure 7a and 7b), in the ex situ process (CAF@ZIF-8 EX)
unstable morphology. To overcome these difficulties, MOFs the contact time was prolonged at 80 °C for 8 h (4.2 1.4%)
are investigated as carriers for conveying loaded cargoes to and in the in situ process (CAF@ZIF-8 IN) the contact time
admired sites due to their plausible size, composition, and was set at 25 °C for 2 h, resulting in a caffeine load of 28.1 ±
functionalized pore surface.134 MOFs as feasible drug delivery 2.6%. Also, to reach a similar result, the contact time must be
materials have the following unique advantages: (i) excessively prolonged about 3 days as t the in situ process was 25 wt % at
adjustable properties and pore size, (ii) elevated drug loading 80 °C. Furthermore, the crystallinity of the material could be
capacity, and (iii) manageable multifunction.128 The MIL damaged due to a longer encapsulation time.128,136 The UV
group is a favorable class of MOFs for drug delivery which is absorption investigation exhibited only caffeine released from
acquired from trivalent metal ions and carboxylate linkers, CAF@ZIF-8 EX (8 h) after 3 days; however, it was constantly
offering a huge pore size (24−25 Å) and applicable surface released from CAF@ZIF-8 IN and CAF@ZIF-8 EX (3 days)
area (3100−5900 m2/g). For example, MIL-53(Fe) and MIL- for 27 days. Lijia and co-workers fabricated an iron-based
53(Cr), two typical MOFs, have been reported to load MOF MIL-101-C4H4 for the encapsulation and release of
ibuprofen (IBU) up to 17.4% and show an extended release DOX.137 First, they prepared MIL-101-C4H4 by using FeCl3
time of 21 days in simulated body fluid (Figure 6).135 MIL- and 1,4-naphthalene dicarboxylic acid through a microwave-
53(Cr) was prepared by using Cr(NO3)2 and benzene 1,4- assisted method. Then, DOX was added dropwise into the
dicarboxylic acid, whereas MIL-53(Fe) was synthesized from MIL-101-C4H4 in an alkaline medium. The DOX was
FeCl3 and benzene 1,4-dicarboxylic acid via a hydrothermal encapsulated in the pores of MIL-101-C4H4, and the loading
approach. capacity was 24.5 wt %, which was completed with a loading
In this survey study, MIL-53(Fe) had optimum loading efficiency of up to 100% (Figure 7c and 7d).
capacities of 14 wt % for busulfan and 30 wt % for caffeine. In the third strategy, the MOF depends on the active
MIL-100(Fe) is also used in drug delivery. Some drugs such as molecular ligands having high loading capacities to avoid
azidothymidine triphosphate (21.1%), DOX (9.1%), cidofovir toxicity compared to inactive molecular ligands, and these
(16.1%), caffeine (24.2%), and IBU (33%) can successfully MOFs could simply reach the combination with the drug by
load by MIL-100. loading another drug.128 Zn−MOFs with ligand ferulic acid
5.2.1. Strategies of Drug Loading. There are primarily 3 have been used as in vitro drug carriers for 5-FU.138 The
sorts of drug loading strategies: one-step encapsulation (in situ maximum loading capacity of 0.388 g/g was achieved when
encapsulation), postsynthesis encapsulation (ex situ encapsu- 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 from 4 to 6. By a pH-responsive DDS, the drug molecule can
5-FU was released due to the degradation of MOF. A pH- be released in the tumor region only. Such a system permits
dependency phenomenon was shown by the release of ferulic rapid and effective drug release inside the cancerous cells
acid and 5-FU at the same time, which showed that 5-FU was without harm to normal cells and hence decreases the systemic
delivered with degradation of {[Zn2(fer)2]}n. disadvantages of chemotherapy in the human body. Therefore,
5.2.2. pH-Responsive Drug Delivery Systems. Conven- this pH-responsive DDS which has the controllable release
tional cancer treatment methods restrict the use of chemo- features of MOFs has been identified as favorable in a
therapy in clinics due to its high toxicity and poor absorption therapeutic application.128 Adhikari et al. reported a feasible
of anticancer medicines.139 The selectivity of an anticancer process to encapsulate DOX into ZIF-8 (highly stable at
drug is responsible for the side effects of chemotherapy. neutral medium) and analyzed its capacity for managed drug
Miserably, most of the conventional formulation cannot release at different pH levels.141 Chowdhuri and co-workers
differentiate between healthy tissue and cancerous tissue in reported a rapid and simple method of an upconversion
the body. The pH of the physiological nature in cancer tissues nanoparticle (i.e., multifunctional nanoparticle) UCNP@ZIF-
was minor compared to that in ordinary tissues.140 Therefore, a 8/FA to release 5-FU anticancer drug at different pH levels.142
pH-responsive drug delivery system was preferred and suitable Schnabel and co-workers recently reported Zn−MOF-74,
for cancer therapy. The pH range of this delivery system is 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 nimesulide, an anticancer drug, was loaded into Fe3O4@MOF-
amount of drug As(III) (153 mg of As2O3 in 1 g of drug- 5. A 20 wt % loading rate was obtained. Furthermore, it was
loaded material) was absorbed into Zn−MOF-74; eventually, revealed that within 11 days nimesulide was fully loaded into
the release process of As(III) shows an obvious pH-responsive physiological saline from Fe3O4@MOF-5. Guan and co-
mechanism. At a temperature of 37 °C, As(III) drug-loaded workers150 discovered an in situ pyrolysis process for the
Zn−MOF-74 was dissolved in PBS, which has two different preparation of γ-Fe2O3@MOFs; the ferric triacetylacetonate
pH values of 6.0 and 7.4. It was shown that As(III) release was was encapsulated inside MIL-53(Al) and ZIF-8. Ibuprofen as a
pH stimulated and occurred more quickly at a pH value of 6.0 standard drug was loaded into γ-Fe2O3@MIL-53(Al) and
than at a pH value of 7.4. released in three stages over the course of 7 days at 37 °C. In
5.2.3. Magnetic Drug Delivery. Recently, magnetic nature the first stage, about 30% of the drug was quickly released in
MOFs have found to be potential candidates for biomedical the first 3 h; after that, during the next 2 days, 50% of the drug
applications due to high surface area and remarkable response was released; last, 20% of the residual drug was released over 5
to magnetic field, faovring to store and release of target drug days. It was concluded that γ-Fe2O3@MIL-53(Al) was a
molecules, which also to allows storing and releasing favorable magnetic material for drug delivery.
pharmaceuticals, while the magnetic particles provide 5.3. Electrochemical Application. As a unit to form a
sensitivity to a magnetic field. A magnetically responsive substance of two different materials, MOF composites have a
drug delivery system permits conceivable excellence in number of vivid execution and electrochemical applications
magnetic targeting, magnetic separation, magnetic hyper- that MOFs cannot accomplish independently, including
thermia, and MRI.144 Magnetic drug delivery is a classic tactic batteries, sensing, supercapacitors, and catalysis. Due to the
to improve drug-loaded therapeutic potency.145 MDD is the diversity of the MOFs, their composites could enhance the
most promising targeted drug delivery system. With the help of characteristics of the MOF and boost the development of
external magnetic conditions, the preparation of magnetic electrochemical applications.151 This is important for the
drugs can be kept at a precise position.146 Magnetic properties effective use of upright and sustainable energy as well as in the
of MOFs allow them to use as highly potential candidates for market of transportable electronic and electric vehicles, urging
drug delivery and bioimaging applications developing contrast the expansion of energy storing materials, mainly electro-
agents in MRI also permit the magnetic formulation to possess chemical energy storage. In light of this, using nanomaterials to
actual time observing because it can be used for bioimaging as store electrochemical energy has proven to be a successful
a contrast agent.147 Fe3O4/Fe2O3 and bimetallic alloys have strategy. Nanosized active materials having mechanical and
been extensively used as a conventional colloidal magnetic electrical properties and a wide surface area are most likely to
nanoparticle. However, there were some unavoidable draw- imbue the space toward discernment of the forth coming
backs like poor loading efficiency, instability, and cytotoxicity generation of energy storage device. To serve different
which restricted the drug delivery application. The customized electrochemical energy storage purposes, many analyses have
MOFs with an integrated magnetic component or coordina- been executed to look for better methodologies for synthesis of
tion of magnetic nanoparticles were favorable substitutes in the materials.152 Several functional materials with zero to two
MDD. It has been proved that magnetic MOFs nanoparticles dimensions combined with MOFs have extensive applications
could precisely convey the drug molecules by physical in electrochemistry, while MOFs fabricated with 3D functional
encapsulation or chemical bonding and shows acceptable materials have hardly been examined and discussed.152
biocompatibility.148 Ke and co-workers discovered a Fe3O4@ 5.3.1. Lithium-Ion Batteries. Thus far, LIBs have been
MOF-5 core−shell nanomaterial fabricated by Fe3O4 magnet- extensively engaged with a movable electrical apparatus,
ite nanorods and a nanocrystal of MOF-MO-5.149 Then, 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 conductive graphene and polymer, the metal shows high
systems have been constructed.163 New types of MOFs with potential as a leading electrode in SCs devices.161 Zhang and
the capacity for structural customization, excess surface area, co-workers established the method of a SDS Zn−Co−S HC
and absorbency to guest molecules have received boundless structure and inspected it as an electrode for SCs.164 The
attention for use in SCs. One of the critical issues of the MOFs elevated surface area, suitable Zn/Co molar ratio of DS Zn−
is their conductivity. Primarily, MOFs show less conductivity, Co−S HC, and weight fraction of the active species resulted in
which is not beneficial to electrochemical devices. However, better performance. The improved capacitance is in excess of
when the MOFs are mixed with conducting materials like 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− 5.4.1. Membrane Filtration. Membrane filtration is the
Co−S maintained a cycling stability of 91% after 10 000 cycles, standard method for separation that permits molecular scale
and single-shelled Zn−Co−S had a 19% capacitance loss under filtration. The particular permeability of the membrane pores is
a similar environment. Generally, the electrochemical capa- used to separate contamination. Notably, the membrane acts as
bility of double-shelled Zn−Co−S was remarkably higher than wall that allows movement of the solvent, inorganic ions, tiny
reported Zn/Co−sulfide-based electrodes for hybrid super- molecules, etc., via a membrane and holds macromolecules and
capacitors. The tactics which are essential for the advancement particles (Figure 10a). The MOF membrane can be further
of supercapacitive performance could be compiled as follows: categorized to enhance the efficiency of filtration like UF, MF,
good dispersion of nanoparticles, existence of a hollow shell NF, and RO.169
porous framework, which allows it to detain nanoparticles, a 5.4.1.1. Microfiltration. Macromolecules, suspended par-
huge channel for smooth movement of electrolyte ions, ticles, and colloids are purified, concentrated, or separated
addition of N2 (nitrogen) or other compounds for optimum from solution using this pressure-driven separation techni-
electrical conductivity, and availability of conductive networks que.170 Microfiltration (MF) retains particles between 0.1 and
so electrons can move easily.152 Ultrathin nanosheets of 1 μm. The MOF composite MF membrane is widely used due
NiCo−MOFs were also used for a high-performance super- to the membrane’s properties being enhanced by MOFs. Ragab
capacitor.165 The authors prepared NiCo−MOF nanosheets and co-workers redesigned a ZIF-8-based PTFE double-layer
by an ultrasonication method using NiCl2 and CoCl2 as the MF membrane to get a ZIF-8/PTFE membrane for removal of
metal salt and terephthalic acid as the organic linker. The micropollutants (progesterone) from wastewater.171 The
effective molar ratio of Ni to Co ions in the synthesis of the outcome was that the adsorption capacity was enhanced
MOF enhanced the electrochemical properties. The electro- about 40% and there was double water permeability (Figure
chemical reversibility and capacitive performance are shown by 10b). This was due to the hydrophobic nature of ZIF-8, which
the nearly symmetric charge−discharge curves at all current minimizes the friction between the membrane surface and
densities. Figure 9b displays the specific capacitances water; hence, there is an increase in the permeability and also
computed from the discharge curves. At the same current the formation of a hydrogen bond between the MOFs and
density, the NiCo−MOF electrode clearly displays an water to enhance the hydrophilicity, thereby increasing the
optimum specific capacitance of 1202.1 F/g at 1 A/g permeability.
compared to the Ni−MOF (840 F/g) and Co−MOF (650.6 5.4.1.2. Ultrafiltration. In this membrane, filtration forces
F/g) electrodes. These results demonstrate the ultrathin such as the concentration or pressure gradients lead to
separation via a semipermeable membrane. Suspended
NiCo−MOF nanosheets’ potential as high-performance super-
particles and solutes with a high molecular weight were
capacitor electrode materials.
trapped, while water and solutes with a low molecular weight
5.4. MOF Membrane for Wastewater Treatment and
pass through the membrane.172 It has small pore size ranging
Water Revival. A MOF made by a metal ion and bridging
from 0.001 to 0.1 mm and requires a high driving force for
ligands has been shown to display preferable membrane
filtration. Ultrafiltration (UF) membranes have been widely
separation performance. It was noted that the MOF could
applied and studied in industry due to the magnificent
increase the selectivity based on its accurately determined pore performance in eliminating suspended nanoparticles, macro-
size, while pores could be controlled in a wide series of guest molecules, bacteria, etc.173 Nowadays, MOFs are mixed with
species shapes and sizes.166 Various types of MOFs are various materials like silica, graphene oxide, titania, etc., instead
available, but the necessary condition for MOFs for use in of existing materials to switch the compatible properties before
wastewater treatment and water revival is the stability of MOFs compounding with polymeric ultrafiltration membranes.
in water. MOFs to be selected as fillers for membranes depend Attention can be moved to the eco-friendly MOF−base
on the following factors: (i) the MOFs have higher selectivity composite membrane with high permeability and stability with
and permeability, (ii) they have uniform and tunable pore antifouling characteristics, making it even more eco-friendly in
structures, (iii) they have greater affinity, and (iv) they can be manufacture application.174 UiO-66 was functionalized by
recycled and reused as fillers in some cases. MOF composite graphene oxide to fabricate UiO-66@GO; then, a UIO-66@
membranes refer to MOFs mixed with polymers as nano- or GO/PES composite membrane was synthesized by PES.175
microparticles to design MOF composite membranes. The outcome indicated that 3.0 wt % of UiO-66 upgraded the
Polymer-based MOFs overcome cooperation linking with the rejection rate, flux, hydrophilicity, and antifouling property, as
selectivity and permeability of the polymeric membrane and shown in Figure 10c. The CA/MOF@GO MOFs composite
also increased the thermal stability and mechanical strength of membrane was prepared using cellulose acetate (CA) as the
the membrane.167,168 MOFs can act as filler TFN membranes base membrane, while MOF@GO was used as a filler.176 The
and MMM to construct MOF-based composite membranes for benefits of MOF@GO fillers mixed with hydrophilic GO and
wastewater treatment and water revival. The ideal MOF MOFs porous structures enhance the preferable membrane
membranes were tested, but the structural defects in the MOF properties. The results exhibited the highest water flux of
materials were unavoidable. Hence, how to design a defect to 183.51 L/m2 h of CA/MOF@GO and better antifouling
be an ideal MOF membrane is currently under debate. The performance. Ultrafiltration is one of the most frequently
MOF particles’ surface properties, MOF membrane, and MOF methods for water decontamination and is also used in reverse
structure limitations have also been studied to be essential osmosis pretreatment.
factors. Due to the versatile pore diameter of the MOF 5.4.1.3. Nanofiltration. Nanofiltration (NF) is a low
membranes, they have excellent application possibilities in pressure-driven membrane method which lies among UF and
water treatment. There are MOF membrane applications such RO as far as its capacity to reject ionic or molecular species.
as membrane distillation, membrane filtration, and membrane The nanofilter may have a larger free space, small pores, or
pervaporation, which are described below.169 nanovoids available for transport.177 NF permits inorganic salts
ACS Omega 2022, 7, 44507−44531
and solvent to go through the membrane to reach the superhydrophobic poly(vinylidene fluoride) nanofiber-based
separation. Due to its efficacy in environmental applications, membrane with 5 wt % of MOF-loaded nanofiber for
the NF method is extensively used in water treatment. Golpour desalination.189 The outcome showed that the water contact
and co-workers prepared PA-MOF/PPSU-GO, a novel MOF angle increased to 138.06 ± 2.18°, the water vapor flux
membrane for nanofiltration for treatment of wastewater increased, and the was a 99.99% NaCl rejection rate (Figure
containing KHI.178 The outcome was that the as-prepared 11). MD is utilized in the food industry and heavy metal
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- Figure 11. PVDF and PV-1 flux and permeate conductivity in
phase Zr−MOF (UiO-66) polycrystalline membrane on an DCMD. Reprinted with permission from ref 189. Copyright 2018
alumina hollow fiber for desalination via a one-step American Chemical Society.
solvothermal synthesis.181 To assess the desalination efficacy
of the membranes as feeds, five different aqueous brine removal in addition to desalination. The use of a photo-
solutions with 0.20 wt % concentrations of NaCl, KCl, MgCl2, thermally enhanced material for membrane distillation could
CaCl2, and AlCl3 were used. The results showed that the increase the energy efficiency of MD. The chemical stability,
membranes had exceptional multivalent ion repulsion for Mg2+ hydrophobicity, and thermal characteristics of the membrane
(98.0%), Ca2+ (86.3%), and Al3+ (99.3%) as well as fine could be improved with the addition of a MOF.
permeability. Furthermore, Hee and co-workers synthesized a 5.4.3. Membrane Pervaporation. Pervaporation (PV) uses
RO MOF composite membrane by combining a PSF a membrane-selective barrier between the feed liquid phase
membrane with HKUST-1[Cu3(BCT2)] MOF.182 The results and the permeate vapor phase in order to separate the two
showed a 33% increase in water flux and a small increase in salt phases. It enables the vaporization of the desired compo-
rejection to 96% (Figure 10e). Recently, CuBDC-NS, a 2D nent(s) of the liquid supply to pass through it. On the basis of
MOF nanomaterial, was discovered as a filler in PA to design a a difference in how quickly each component moves across the
suitable TFN membrane.183 The results showed a 50% membrane, components can be separated.190 This is due to the
increase in water flux through the TFN membrane and a fact that the driving force for the vapor pressure in PV is
50% reduction in specific reverse solute flux using 1.0 M NaCl different from that for membrane distillation. Also, PV is less
for AL-FS mode (Figure 10f). A novel area of interest in MOF energy consuming and more energy effective than MD because
repurposing of RO and FO membranes is the control of the of the feed solution and permeate vapor. Typically, the best
MOF size to alter the performance of the membrane and permeate flux and separation factor are provided by the PV
increase the filter efficiency. membrane. Organic solvents in water are primarily removed
5.4.2. Membrane Distillation. Membrane distillation (MD) and recycled using a PV membrane. As the PV membrane can
is an effective separation technique that can reduce water be either organophilic or hydrophilic depending on the
energy stress in an environmentally friendly manner. To drive application, it is also employed for recovery of organic
desalination, separate nonvolatile pollutants, or extract other solvents.191 A superhydrophobic MAF-6 into PDMS was
components, MD requires low-grade thermal energy. In MD, reported to design MMM for the recovery of ethanol.192 MAF-
an aqueous solution’s vapor travels through a hydrophobic 6’s hydrophilicity and high porosity increased the membrane’s
membrane and then condenses on the other side of the permeability, selectivity, and stability. When MAF-6 was
membrane to produce a high-quality distillate.184 The driving loaded to MMM, the hydrophobicity reached 15 wt %.
force behind the separation is the vapor pressure on the two According to experimental findings, the MMM membrane
sides of hydrophobic porous membrane.169 DCMD, AGMD, shows remarkable hydrophobicity when MAF-6 loading was 15
SGMD, and VMD are four forms of MD currently wt %, resulting in the highest flow of 1200 g/m2 h and a
available.185,186 Thermostability, hydrophobicity, improved separation factor of 14.9. For the purpose of developing an
thermal conductivity on the feed side, and low mass transfer MMM for the recovery of 1-butanol, they also discovered a
resistance are all characteristics of MD membranes.187 In order ZIF-8 particle that was reconstructed through silanization into
to create new MOF composite membranes for desalination, PDMS.193 The results revealed that these particles increased
Zuo and co-workers discovered an alumina-based MOF the 1-butanol flow 85% and had a 34% separation factor
membrane.188 Because of the MOF functionalization, hydro- (Figure 12a). Since recovering organic solvents is the main use
phobicity was increased. Fan and co-workers developed a of pervaporation, the stability, selectivity, hydrophobicity, and
ACS Omega 2022, 7, 44507−44531
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, fixation,203 cyano silylation,204,205 etc. More could be learned
MOF-based MMM was also used for water decontamination. about the potential uses of MOFs in sustainable green catalysis,
Worood and co-workers prepared a MMM that contained including biocatalysis, solvent-free catalysis, designing catalysts
UiO-66-NH2 MOFs as the adsorbent and CA as the polymeric for reactions in environmentally friendly solvents, and
matrix to prepare MOF@CA MMM for the removal of water enhancing the recyclability of catalysts. The application of
contamination.194 First, they prepared UiO-66-NH2 by using sensing has recently drawn some study interest. For sensing
ZrCl2 as a metal salt and 2-aminoterephthalic acid as an purposes, carbon nanoparticles and metal oxide nanocompo-
organic linker. Then, freshly prepared UiO-66-NH2 crystals sites are utilized.
were added to the cellulose acetate solution via stirring for 3 h.
The solution was transferred into a glass Petri dish and dried 6. CONCLUSION AND FUTURE PERSPECTIVES
overnight at room temperature. The synthesized MOF@CA This report has covered the classification, nomenclature,
MMM showed excellent performance in the removal of organic synthesis methods, influencing factors, potential applications,
dye (methyl orange and methylene blue) and dichromate ions as well as the biomedical applications of the metal−organic
in comparison to the control polymer cellulose acetate framework. It has explained how MOFs can be classified and
membrane (Figure 12b). Hence, MOF-based membranes synthesized with interesting characterization. Although the
proved the approachability of the MOF nanocage immobilized conventional hydro/solvothermal synthesis method was
within the MMM. The effective application of such a strategy adequately used in MOF synthesis, unconventional and new
to develop novel membrane materials for wastewater treatment methods like electrochemical, mechanochemical, sonochem-
applications should be based on the optimum hybridization of ical, microwave-assisted, etc., methods are just materializing in
the chosen polymer matrix and the MOF filler to address the this extent.206 These are crystalline porous materials in which
required conditions in a given context. the metal is fixed in place to fabricate a porous and rigid
Other applications include catalytic application, which have geometry and uses various bridging ligands.61 Alternative
been extensively employed for various transformations such as methods lead to the MOFs having various properties. Potential
Friedel−Crafts reactions,195,196 condensation reactions,197,198 applications of MOFs have also been discussed within the
oxidations,199,200 coupling reactions,201,202 carbon dioxide energy industry, such as next-generation rechargeable batteries
ACS Omega 2022, 7, 44507−44531
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, [email protected]
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
ACS Omega 2022, 7, 44507−44531
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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1. INTRODUCTION specific design of hollow-structured materials can give an entire

through ligancy, the analytic geometry of the inorganic

Figure 2. Organic molecules as linkers used for the preparation of MOFs.

Figure 3. MOFs with various metal nodes and organic linkers.

Scheme 1. Microwave-Assisted Synthesis of MOF Structures

Scheme 2. Electrochemical Synthesis of MOF Structures

Scheme 3. Conventional Solvothermal Synthesis of MOF Structures

Scheme 4. Mechanochemical Synthesis of MOF Structures

Scheme 5. Sonochemical Synthesis of MOF Structures

reduced). Férey’s group reported a hydrogen capacity of 3.8 wt

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