Overview of Metal Organic Frameworks

Fatemeh Ganjali and Simindokht Zarei-Shokat

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1 Abstract A new class of hybrid material known as a metal–organic framework
2 (MOF) is created when an organic molecule coordinately bonds with an inorganic
3 molecule (often high nuclearity metal clusters or transition metal ions) to form a
4 framework or cage-like structure. The MOFs are a particular kind of coordinate poly-
5

7
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mers (CPs). The remarkable crystallinity of MOFs, which distinguishes them from
noncrystalline CPs, is provided by the periodic arrangement of metal and organic
linkers. MOFs are typically classified as crystalline, amorphous, luminescent, nano-,
8 and bio-MOFs depending on the crystalline shape and synthetic methods. MOFs
9 have received substantial attention as a highly flexible substrate for functional appli-
10 cations in a variety of research domains due to their extraordinarily high surface area,
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11 enormous porosity, tunable pore size, and flexible functionality.

12 Keywords Metal–organic frameworks · Synthesis · Ligand · Coordination ·

13 Porosity
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14 1 Introduction

15 Porous materials have drawn a lot of interest during the past 50 years, including
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16 zeolites, coordination polymers,1 and metal–organic frameworks.2 Their porosity,

17 which enables the migration of guest molecules into the bulk structure, is an intriguing
18 property. The selection of the guests to be incorporated depends on the form and
19 size of the pores. According to Yaghi et al., MOFs are porous structures made of
20 coordinative bonds between organic bridging ligands and metal ions [1].
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1 CPs.
2 MOFs.

F. Ganjali · S. Zarei-Shokat (B)

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Catalysis and Organic Synthesis Research Laboratory, Department of Chemistry, Iran University
of Science and Technology, 16846-13114 Tehran, Iran
e-mail: simindokht.zarei@gmail.com
F. Ganjali
e-mail: Fatemeh.ganjali1373@gmail.com; Fatemeh_ganjali@chem.iust.ac.ir

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 1

A. Maleki and R. Taheri-Ledari (eds.), Physicochemical Aspects of Metal-Organic
Frameworks, Engineering Materials, https://doi.org/10.1007/978-3-031-18675-2_1

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 2 F. Ganjali and S. Zarei-Shokat

21 As secondary building units3 or metal-containing units4 are anchored with organic

22 linkers by coordination, open frameworks with extraordinary properties including
23 permanent porosity, a stable framework, a large surface area, and large pores are
24 produced. Long organic linkers give MOFs a lot of storage space and a lot of
25 adsorption sites, which results in porosity. Additionally, they possess the capacity to

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26 purposefully alter and functionalize their pore structure [2].
27 The synthesis of MOF-5 (Zn4 O (bdc)3 ; bdc = terephthalate) and HKUST-1
28 (Cu3 (btc)2 ; btc = 1,3,5-benzenetricarboxylate) with high porosity and low pressure
29 gas sorption, followed by the formation of chromium (III) terephthalate (MIL-101)
30 with high chemical stability, served as benchmarks in the history of MOFs. Several

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31 isostructural analogs of Mg-MOF-74, referred to as IRMOF-74I to IRMOF-74XI,
32 have large pore apertures to accommodate protein, and NU110E with acetylene
33 expanded hexatopic linker has the highest experimental Brunauer–Emmett–Teller
34 (BET) surface area of any porous material reported to date (7140 m2 g−1 ) among
35 porous materials. Table 1 provides some illustrations of MOFs and their applications.

36 2 Chemical Composition
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37 The kind of the linker is one fundamental factor to take into account when determining
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38 what qualifies as a MOF and what does not. The name “metal–organic framework”
39 implies the need for a metal, but the nature of the organic components has caused
40 considerable misunderstanding, and some people have chosen to ignore the problem
41 in favor of maintaining ambiguity [16]. Typically, substances having carbon–carbon
and/or carbon–hydrogen bonds are referred to as organic compounds. Prussian blue
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42

43 with cyanide ligands is not a MOF in light of this argument. Prussian blue with
44 cyanide ligands is not a MOF in light of this argument. Inclusion of polymeric metal
45 carbonates, etc. follows an argument that it happens swiftly. In contrast, because
46 the linkers are regarded as organic compounds even in the absence of C–H bonds,
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47 framework structures comprising metal-oxalates, metal tetrafluoroterephthalates, etc.

48 belong to the class of MOFs. To distinguish MOFs from simply organic or inor-
49 ganic polymers, they have also been referred to as organic–inorganic hybrids [17,
50 18]. However, the term “hybrid” describes a species that is created by fusing two
51 or more creatures with various characteristics. By combining two or more phases,
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52 usually at the nanoscale, hybrid materials are created. According to some reports,
53 porous CPs and MOFs have been used as hosts to enclose or graft discrete molecular
54 species, nanoparticles, organic polymers, etc., creating composite or hybrid mate-
55 rials that benefit from the functional traits of both the host and guest components
56 [19, 20]. However, a straightforward MOF should not be referred to as an inorganic–
organic hybrid material since it is a chemically separate entity that is produced by
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57

58 coordination bonding between metal ions and organic linkers [21].

3 SBUs.
4 MCUs.

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 Table 1 Some examples of MOFs and their applications
Application MOF Metal Ligand Year References
Drug delivery MIL101[Cr3 O(OH, F, H2 O)3 (1,4-bdc)3 Cr 1,4-benzenedicarboxylate moieties (bdc) 2006 [4]
and MIL-100 or H3btc: Benzene-1,3,5-tricarboxylate
Methane Storage MOF-5 Zn4 (1,4-bdc)3 Zn Bdc 2002 [5, 6]
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Adsorption and storage HKUST (Hong Kong University of Science Cu H3btc 2006 [7]
and Technology)-1 Cu2 (H2 O)2 (CO2 )4
Adsorption and storage IRMOF-9 Zn4 O (bpdc)3 Zn 4,4 -biphenyldicarboxylate (bpdc) 2006 [7]
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Adsorption and storage MOF-74, Zn2 (C8 H2 O6 ) Zn 2,5-dihydroxybenzene-1,4- dicarboxylic 2006 [7]
acid
– (In) MIL-68-NH2 or IHM-2 In bdc-NH2: 2- aminoterephthalates 2011 [8]
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529312_1_En_1_Chapter  TYPESET
Drug delivery metal–organic Zn (bix) sphereswith Zn Bix: 1.4-bis (imidazol-1- ylmethyl) 2010 [9]
Overview of Metal Organic Frameworks

encapsulated DOX [DOX/Zn(bix)], SN-38 benzene

[SN-38/Zn(bix)], CPT [CPT/Zn(bix)] and

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DAU [DAU/Zn(bix)] Doxorubicin (DOX),
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SN-38, camptothecin (CPT) and
daunomycin (DAU)
Soft coupling– deprotection sequence (In) MIL-68-NH-ProFmoc and (In) In Amino acid such as L-proline (Pro-OH) 2011 [10]
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MIL-68-NH-Ala-FmocIn and D-alanine (Ala-OH)
*fluorenylmethyloxycarbonyl
group(Fmoc), abase-label protecting group
for amines
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Antibacterial Cu-BTC(MOF-199) Cu H3 btc 2014 [11]
Highly potent bacteriocidal activity Co-TDM Co H8 tdm: tetrakis [(3.5- dicarboxyphenyl)- 2012 [12]
oxamethyl] methane
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Delivery of nitric oxide MIL-100(Fe or Cr) and MIL-127(Fe) Fe, Cr or Fe Tricarboxylate or tetracarboxylate 2014 [13]
Antibacterial Ag2 (O-IPA) (H2O)·(H3O) and Ag5 Ag HO-H2 ipa = 5- hydroxyisophthalic acid 2014 [14]
(PYDC)2 (OH) and H2 pydc = pyridine-3, 5- dicarboxylic

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acid
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Adsorption of CO2 over N2 Mn3 (HCOO)6 ·DMF Mn 3-nitrophthalic acid (H2 npta) and 2014 [15]
4.4 -bipyridine (4.4 - bipy) 2014
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 4 F. Ganjali and S. Zarei-Shokat

59 3 Porosity

60 The amount of holes in a material is related to its porosity, which is commonly

61 expressed by the volume of solvent-accessible spaces or by the surface area derived
62 from gas adsorption isotherms. The IUPAC concept of “potential void” has been

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63 proposed as a prerequisite for classifying a coordination-based polymer as a MOF
64 [22]. The phrase “potential void” describes the breathing behavior (or flexibility) of
65 certain compounds’ frameworks, but not that of nonporous frameworks. The size and
66 chemical build of the guests determine the porosity, which is not an absolute feature
67 (close-packed spheres occasionally contain spaces that can be filled). Positrons are

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68 always able to locate porosity, therefore a substance that is porous to one gas may
69 act as nonporous to other gases. In order to balance the charges on the ionic frame-
70 work structures of several of these solids, guests with opposing charges are present
71 in their cavities. These compounds have the ability to exchange ionic species for
72 counterionic guests, although they may act impermeable to any neutral guests or
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ions carrying the same charges as the frameworks [23]. The next generation of func-
tional materials in the disciplines of energy materials, optoelectronics, ferroelectrics,
multiferroics, batteries, magnets, etc. are presently developing as nonporous MOFs
76 with high density [24]. Since an arbitrary pore size would have to be specified and
77 none can be justified on the basis of science, porosity or “potential void” should not
be used as a parameter to determine whether or not a coordination molecule is a
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78

79 MOF.

4 Metal Biomolecule Frameworks (Bio-MOFs)

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81 Biomolecules are plentiful and spontaneously occurring. They produce structurally

82 varied, physiologically compatible MOFs because they are flexible, stiff, and
83 cost-effective with various coordination sites. Additionally, non-toxic endoge-
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84 nous cations (such Ca, Mg, Fe, and Zn) and ligands made of naturally occurring
85 compounds or biomolecules have both been used to make MOFs [25]. Typically,
86 these Bio-MOFs are biocompatible and appropriate for use in biomedical applica-
87 tions. Several therapeutic benefits (anti-allergic, anti-inflammatory, antibacterial,
88 and anticarcinogenic actions) are also linked to these combinations of natural ligands
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89 and endogenous cations [26]. Examples of Bio-MOFs and their uses are provided
90 in Table 2. These nontoxic, ecologically friendly, and biologically compatible metal
91 ions and organic linkers serve as the building blocks for these biologically and envi-
92 ronmentally compatible MOFs, which are created and developed based on particular
93 composition requirements. Biomolecules like amino acids, peptides, proteins,
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94 nucleobases, carbohydrates, and other naturally occurring substances like cyclodex-

95 trins, porphines, and some carboxylic acids are emerging building blocks for the
96 creation of metal–biomolecule frameworks with novel and intriguing properties and
97 applications that cannot be achieved through the use of conventional organic linkers.

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 Table 2 Some examples of Bio-MOFs and their applications
Application Bio-MOF Metal Ligand Year References
Ar and CH4 sorption [Cu(trans-fum)] Cu Fum: Fumaric acid 2001 [27]
Reversible H2 O [Ni7 (suc)6 (OH)2 (H2 O)2 ] 2H2 O Ni Suc: Succinic acid 2002 [28]
sorption/desorption
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– [Ni7 (suc)4 (OH)6 (H2 O)3 ] 7H2 O Ni Suc 2003 [29]
[Mn3 (HCOO)6 ]·(CH3 OH)·(H2 O) Mn Formic acid 2004 [30]
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Selective CO2 [Mn3 (HCOO)6 ] (CH3 OH) (H2 O) Mn Formicacid 2004 [31]
and H2 sorption
Adsorption Fe3 O (MeOH)3 Fe Fum 2004 [32]
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(fum)3(CO2 CH3 )]0.4.5MeOH
Overview of Metal Organic Frameworks

1.3-Butanediol [Ni2 o(L-Asp)H2 o] 4H2 O Ni Amino acid LAsp:L-aspartic 2004 [33]

sorption acid

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Enantioselective Zn2 (bdc)(L-lac)(DMF) Zn bdc: 1,4 2006 [34]
separation and benzendicarboxylic
catalytic acid and L-
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lac:Lactic acid
CO2 sorption [Ni2 (L-Asp)2 (4,4 -bipy)] 2H2 O Ni L-Asp and 2006 [35]
4,4 -bipy: 1,2-bis
(4-pyridyl)ethane
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H2 sorption CO2 (L-Asp)2 (4,4 -bipy)]· 2H2 O Co L-Asp and 4,4 2008 [36]
-bipy
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Heterogeneous Ni2 (L-Asp) (4,4 -bipy)·(HCl)1.8(MeOH) Ni L-Asp and 4,4 -bipy 2008 [37]
Asymmetric catalysts for
the methanolysis
of rac-propylene

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oxide
(continued)
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Table 2 (continued)
Application Bio-MOF Metal Ligand Year References
Heterogeneous Cu2 (L-Asp)2 (bpe) (HCl)2 (H2O)2 Cu L-Asand bpe: 2008 [37]
asymmetric 1,2-bis(4-pyridyl)ethane
catalysts for
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the methanolysis
of rac-propylene
oxide
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Cation exchange capabilities, Zn8 (Ade)4 (bpdc)6 O 2Me2 NH2 8DMF Zn Nucleobases 2009 [38]
including 11H2 O Adenine:Ade
cationic drugs and bpdc:
and lanthanide biphenyldicarboxylate
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529312_1_En_1_Chapter  TYPESET
ions
Selective Co2 (Ade)2 (CO2 CH3 )2 2DMF 0.5H2 O Co Ade 2010 [39]

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CO2 . sorption
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Drug delivery Fe3 O (MeOH)3 (fumarate)3 -(CO2 CH3 )] 4.5 - Fumarate and C6 H4 O8 is 2010 [40]
and imaging MeOH and [Fe3 O(MeOH) galactarate
(C6 H4 O8 )3 C1] 6MeOH
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Therapeutic agent BioMIL-1 Fe Nicotinic acid (pyridine-3- 2010 [41]
carboxylic acid, also called
niacin or vitamin B3)
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Reversible [Zn(glyAla)2 ] (solvent) Zn Peptide,Glycine-adenine 2010 [42]
flexible structure;
CO2 , MeOH and
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H2 O sorption
(continued)

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F. Ganjali and S. Zarei-Shokat
 Table 2 (continued)
Application Bio-MOF Metal Ligand Year References
(γ-CD) (KOH)2 K Saccharides 2010 [43]
γ -CD: cyclodextrins
Inclusion of Rb 2010 [43]
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(γ-CD) (RbOH)2 γ-CD
several molecules γ-CD is a (chiral) cyclic
(e.g. Rhodamine oligosaccharide composed of
B,4-phenylazoplenol,etc.) eightR-1,4- linkedD-
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glucopyranosyl
(R-1,4-D-Glup)
Highly selective CD-MOF-2 Rb γ-CD 2011 [44]
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529312_1_En_1_Chapter  TYPESET
adsorption of CO2
Overview of Metal Organic Frameworks

Photostable O2 sensor Zn8 (Ade)4 (bpdc)6 O 2Me2 NH2 ] Zn and Ade and bpdc 2011 [45]
loadedwith lanthanidecations (Tb(III), lanthanide

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Sm(III), Eu(III)
and Yb(III))
M(II/III)Gallates Fe,Mn, Co H4 gal: gallic acid 2011 [46]
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and Ni
Porous α-CD-MCF Rb α-CD 2012 [47]
R-cyclodextrin
(R-CD),comprised of
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sixR-1,4-
D-Glupresidues
portrayed in
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their stable
4C1 conformations
Adsorption CD-MOF-1and CD-MOF-2 CD-MOF-3 K, Rb and Cs γ-CD 2012 [48]

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(continued)
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Table 2 (continued)
Application Bio-MOF Metal Ligand Year References
Drug storage Bio-MOF-100 Zn Ade 2012 [49]
and release
or for the
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immobilization
and organization
of large biomolecules
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MIL-151 to -154 Zr H4 gal 2014 [50]
Antibacterial Bio-MIL-5 Zn AzA: azelaic acid 2014 [51]
Antioxidant carrier Mg(H4 gal) Mg H4 gal 2015 [52]
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529312_1_En_1_Chapter  TYPESET
Inclusion and loading the CD-MOF-1 Na β-CD:cyclodextrins 2015 [53]
drug molecules

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Electrochemical MOF-525 Zr 2015 [54]
EC H4 tcpp: meso-tetra
Nitrite detection (4-carboxyphenyl)
Ammonia uptake Al-PMOF Al H4 tcpp 2015 [55]
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Highly active [Zn(ain) (atz)]n Zn Hatz: 5- 2016 [56]
anti-diabetic aminotetrazole
activity and Hain: 2-
amino-4-isonicotinic
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F. Ganjali and S. Zarei-Shokat
 Overview of Metal Organic Frameworks 9

98 5 MOFs Synthesis

99 The creation or breaking of bonds requires energy, and this phenomena is true for
100 the synthesis of MOFs as well because it involves the bonding of organic linkers
101 and metal oxides. The primary goal of MOF synthesis is to produce distinct inor-

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102 ganic building components that do not include organic linker breakdown [58]. For
103 the synthesis of MOFs, any device that can provide a controlled quantity of heat
104 will work. For instance, heat may be delivered from ovens, microwaves, mechan-
105 ical ultrasound, electric potential, and electromagnetic wave radiation, among other
106 sources. The sort of energy or source used determines the nature of the MOFs that are

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107 produced, and the synthesis process determines the MOFs’ characteristics. Multiple
108 MOF synthesis pathways are essential due to their variety of characteristics. The
109 main characteristics of the generated MOFs, such as size distribution, shape, and
110 particle size, determine their suitability or application. As a result, the type of heat
111 energy generated during its formation and the heat source employed both affect the
112

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porosity of the MOFs that are produced. Even though the coordination of metal
clusters with organic ligands to create MOFs looks simple, getting the desired struc-
ture is really difficult. The kind of MOFs manufactured is influenced by process
115 variables (time, temperature, and pressure) as well as compositional characteristics
116 (solvent, pH, linker substituent, and metal ion concentration). High surface area, high
porosity, and common starting materials, especially for their ligands, are a few essen-
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117

118 tial characteristics that make MOFs incredibly attractive to researchers working in
119 multidisciplinary fields. Even though the same reactive mixture (a metal source, an
120 organic ligand, and a solvent) is employed to create MOFs, reaction duration, particle
121 size, yield, and morphology all have an impact on the final structure. Therefore,
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122 the various MOF synthesis techniques are much required. Some synthesis methods
123 are excellent choices for the large-scale process. Conventional solution, diffusion
124 synthesis, solvothermal synthesis, microwave synthesis, sono-chemical synthesis,
125 electrochemical synthesis, and iono-thermal synthesis are a few of the approaches
126 employed for MOF synthesis (Fig. 2).
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127 6 Conclusion
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128 MOFs have a wide range of uses, such as catalysts, sensors, storage and separation
129 devices, and drug delivery systems. Nanodrug carriers for antitumor and anti-HIV
130 medications may be made from non-toxic nano-MOFs with customized cores and
131 surfaces (biomedicine, nontoxic, drug). In contrast to their counterparts containing
132 conventional organic linkers, MOFs with biomolecules as organic linkers are still in
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133 the nascent stage. However, biomolecules give MOFs easy recyclability and biolog-
134 ical compatibility. They also provide structures with distinctive qualities including

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Fig. 1 Illustration of MOF formation and factors affecting MOF synthesis. This figure was adapted
by permission from: Trends in Food Science and Technology, (2020), 104, 102–116 [3]

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Fig. 2 Different methods of MOF synthesis, a Sono-chemical synthesis method, b Conventional

solution method, c Diffusion synthesis method, d Iono-thermal process method, e Microwave
synthesis method, f Electrochemical synthesis method, and g Solvothermal synthesis method. This
figure was adapted by permission from: Trends in Food Science & Technology, (2020), 104, 102–116
[3]
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135 chirality and particular recognition, separation, ion exchange, and catalytic capabil-
136 ities, as well as bio-inspired features. Future potential for MOFs’ structures, charac-
137 teristics, and applications in various domains may arise from a greater knowledge of
138 the chemistry involved in their creation.

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