Journal of Composites and Compounds 5 (2023) 25-37

Available online at www.jourcc.com

Journal homepage: www.JOURCC.com

A critical review about metal organic framework-based composites:

Potential applications and future perspective
Hicham Meskher a*

a
Division of Process Engineering, College of Applied Science, Kasdi-Merbah University, Ouargla, 30000, Algeria
a

ABSTRACT ARTICLE INFORMATION

The properties of metal-organic frameworks (MOFs), a potential class of porous crystalline materials with a wide Article history:
range of uses, depend on their structural details, including compositions and architectural designs. Through func- Received 17 December 2023
tionalization and their interaction with other nanomaterials, MOFs' structure and design have undergone changes Received in revised form 26 January 2023
as a result of their extensive research. Numerous outstanding evaluations on single MOFs, MOF-based composites Accepted 11 March 2023
created through conjugation with non-MOF materials, and their derivatives have summarized the developments
in the field of MOFs. A thorough examination of MOFs and their combination is, however, lacking. In this per-
spective, we present a current and thorough description of the accomplishments of MOF-based hybrids below. Keywords:
First, a description of the synthetic strategy/formation process is provided to illustrate how host and visitor MOFs Metal organic framework
interact. The structural diversity in MOF-based systems is then thoroughly examined to show how MOF systems Synthetic strategy
enable advancements in abased composites for a variety of applications, particularly in the medical and environ- Application
mental fields. Finally, we present our personal opinions on the difficulties and potential paths for the development Nanohybrids
of MOFs materials. Metal nanoparticles
©2023 UGPH.
Peer review under responsibility of UGPH.

Table of contents
1. Introduction ........................................................................................................................................................................................................................................... 25
2. MOF-based composites ........................................................................................................................................................................................................................ 26
3. Synthesis ............................................................................................................................................................................................................................................... 27
3.1. Surface modified encapsulation ....................................................................................................................................................................................................... 27
3.2. In situ generation in MOF cavities ................................................................................................................................................................................................... 27
3.3. Self-sacrificed template method ....................................................................................................................................................................................................... 28
3.4. Step-by-step construction of the sandwich-like heterostructure ...................................................................................................................................................... 28
3.5. One-pot synthetic method ................................................................................................................................................................................................................ 29
4. Applications .......................................................................................................................................................................................................................................... 29
4.1. Gas storage and separation .............................................................................................................................................................................................................. 29
4.2. Catalysis ........................................................................................................................................................................................................................................... 29
4.3. Sensing ............................................................................................................................................................................................................................................. 30
4.4. Water treatment and purification ...................................................................................................................................................................................................... 31
4.5. Pharmaceuticals and Biotechnology ................................................................................................................................................................................................ 31
4.6. Environmental remediation .............................................................................................................................................................................................................. 32
5. Conclusion and Future Prospects .......................................................................................................................................................................................................... 32

organic frameworks (MOFs), a family of crystalline organic-inorgan-

1. Introduction ic hybrid compounds [1-4]. The structure of the framework, inorganic
metal centers, and organic ligands are the three primary components of
Bivalent or trivalent aromatic carboxylic acids or N-containing ar-
MOF. If MOFs were created by expanding zeolite topology, their inor-
omatics are frequently utilized to build frameworks with gold, zinc,
ganic and organic structures would have larger pores and higher porosity
copper, chromium, aluminum, zirconium, and other elements in metal
than zeolites. The enlarged size of inorganic SBUs and the network’s
* Corresponding author: Hicham Meskher; E-mail: [email protected]
DOR: 20.1001.1.26765837.2019.1.1.4.3
https://doi.org/10.52547/jcc.5.1.5 This is an open access article under the CC BY license (https://creativecommons.org/licenses/by/4.0)
 26 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37

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Fig. 2. Scheme representing the synthesis of fcc Ru NPs via PCC-2 as the tem-

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Fig. 1. One-pot synthesis of poly(ethylene glycol) modified zeolitic imidaz-
olateframework-8 nanoparticles: Size control, surface modification and drug plate. Reproduced with permission from Elsevier [37].
encapsulation. Reproduced from Elsevier [35]. works (MOFs) are created when core metal ions or clusters self-assem-
ble with bidentate or multidentate organic ligands using coordination
dimensions caused by big metal clusters are the causes of the huge pore
bonds [1,10]. Since their discovery in the early 1990s, MOFs have
size. Additionally, a combination of high porosity and longer organic
been the subject of intense research because of their highly organized
ligands that benefit big pore width account for the length of the link
porosity, extraordinarily high internal surface areas, and adaptable ar-
between inorganic SBU. When various metal centers and ligands are
chitectures. As a result, MOFs swiftly gained popularity as materials for
used to create MOFs as molecular building blocks, the resulting flexibil-
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almost two decades [11]. Up to this point, significant efforts have been
ity allows for the modification of both physical and chemical properties
made to create MOFs with novel structures and properties and to explore
[5]. MOFs are synthesized through various procedures such as surface
their potential uses in a variety of industries, including gas adsorption/
modified encapsulation, in situ generation in MOF’s cavities, self-sac-
separation, catalysis, sensors, drug delivery, magnetic materials, and op-
rificed template method, microwave assisted methods, room tempera-
tical devices [12-14].Unfortunately, there are several instances where
ture based procedures, step-by-step construction of the sandwich-like
the performance of MOF materials is less than ideal, and there is still
heterostructure, and one pot synthetic method [2,3,6,7]. Due to MOFs’
much work to be done to increase their applicability [15].
exceptional qualities, these materials are now widely used in a variety of
MOFs have advantages over conventional porous materials in terms
e-
fields, including medication delivery, sensing, and gas storage [8,9]. The
of shape and characteristics, allowing open channels to be constructed
syntheses of MOF-based composites or their use in the catalysis or sens-
and carefully tuned utilizing various metal nodes and organic ligands in
ing domains were the focus of many outstanding publications that dis-
accordance with intended uses [16]. MOFs are excellent host platforms
cussed the synergistic effect between MOFs. In contrast, it is currently
for the immobilization or encapsulation of various functional materials,
unclear how the functions of MOF component parts relate to their actual
such as nanoparticles (NPs), quantum dots, polyoxometalates, enzymes,
applications. In fact, according to some studies, MOFs’ distinct internal
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and polymers, because of their structural diversity and adaptability [17-

structures and properties—rather than those of other integrated func-
19]. As a result of the materials’ synergy, MOF composites always dis-
tional materials—are the primary cause of the improved performances
play significantly improved or even unique features when compared to
and expansion of MOF-based composite functionalities. Therefore, it is
single-component materials [20].
crucial to clarify the function of MOFs in composites in order to com-
Technically, the constrained environment produced by the MOF
prehend how the structure and functionality of materials based on MOFs
cavities might significantly increase the catalytic activity of embedded
relate to one another.
NP catalysts [21]. MOF composites may be used to create sensors that
This paper summarizes current developments in MOF-based com-
can identify the size of molecules by utilizing the barrier effect in MOF
posites in an effort to better understand the structure-performance rela-
channels on the flow of foreign molecules [22]. Additionally, it was dis-
tionship of MOF-based composites, with a focus on the practical uses of
covered that after being enclosed in MOFs, fragile enzymes may display
MOF components. First, common techniques for producing MOF-based
great tolerance under challenging circumstances while maintaining high
composites are discussed, along with benefits and drawbacks. Next, ac-
activity [6,15,23]. In order to further improve their performances and
cording to the functions of MOF components in MOF-based composite
broaden their applications, MOF-based composites have drawn growing
applications, the impact of internal composition, structures, and proper-
research attention. As a result, significant effort has gone into design-
ties of MOFs as well as external encapsulation status characteristics on
ing and building different MOF-based composites. However, despite
the performance of composites is discussed, with a focus on their use
the great progress, achieving functionality between the MOF host and
in the medical field and environmental remediation. Then, contempo-
guest species is still challenging for specific applications of MOF-based
rary problems with these composites are given and discussed. To further
composites. Hence, it is vital to identify the structural–functional rela-
pique the curiosity of chemical aficionados, we think that the review will
tionship in MOF composites to efficiently and directionally synthesize
give readers a better grasp of MOF-based composites for more carefully
specific MOF composites for particular applications.
managed manufacturing and application.
The synergistic relationship between MOFs and other functional
materials has already been covered in a number of outstanding reviews
2. MOF-based composites [26,27]. The majority of them concentrated on the creation of MOF-
based composites or on using them in catalysis or sensing sectors [28] .
The crystalline porous materials known as Metal-Organic Frame- In contrast, it is currently unclear how the functions of MOF component
 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37 27

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Fig. 3. Schematic of ZnO@ZIF-8 nanorods made using the self-template method Fig. 4. For the first time, a method for creating novel materials for sensing vol-
is shown in Fig. 3(a). (b) A SEM image of ZnO@ZIF-8 nanorods, and (c) an atile organic molecules is proposed, combining metal oxides and metal-organic
XRD pattern. Reproduced with permission from ACS [39]. frameworks.
parts relate to their actual applications. In fact, some research revealed MOF will be grown on the surface of the prepared NPs creating great
that instead of the properties of other integrated functional materials, the lattice structure barriers between MOFs and encapsulated materials,
better performances and expansion of MOF-based composite functions leading to self-nucleation of MOFs instead of forming the encapsulation
mostly originate from the unique internal structures and properties of structure. To overcome such barriers, structure-flexible materials have
MOFs [29]. In order to better comprehend the relationship between the been used bridges to connect MOFs with encapsulated materials.
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structure and function of MOF-based materials, it is crucial to clarify the For instance, to correct the lattice mismatch at NP@MOF surfaces,
role of MOFs in composites. several authors treated NPs with surfactants PVP and CTAB afterwards
Many different combinations of nanomaterials and MOFs can be [30]. In addition to surfactants, metal oxides or hydroxides may be used
used to create MOFs-based composites, which enable the achievement to alter NPs and build MOFs [31,32]. NPs of different shapes and sizes
of a wide range of functions and characteristics. Composites made from can be enclosed inside MOF shells using encapsulation. Other materi-
MOFs are appealing for a variety of applications due to their many ben- als, including carbon-based compounds, polymers, and even enzymes,
efits. Several of these benefits include: might be employed in place of these nanoparticles to modify the MOFs
High surface area: Composites based on MOFs have high surface surfaces using this technique [33,34].
e-
areas, making them suitable for catalytic and adsorption processes. Unfortunately, this technique could be time-consuming which require
Porosity: Composites based on MOFs are porous, which makes more effort to find new rots and alternative to improve this technique. In
them good for storing and separating gases. this context, a study reported a simple and rapid synthetic method that
Tunable characteristics: A wide range of functionalities and prop- combines the size control of ZIF-8 NPs and their surface modification
erties can be attained by synthesizing MOFs-based composites from a of PEG at the same time. Monovalent amino PEG (PEG-NH2) was used
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variety of metal ions and organic ligands. as capping agent to control the size of ZIF-8 and simultaneously realize
Chemical stability: Composites based on MOFs may exhibit strong surface modification through coordination interaction. The size of ZIF-8
chemical stability, making them appropriate for usage in challenging was tuned in a board range. The coated NPs showed intact crystalline
conditions. structure with improved colloidal stability. By further adding the anti-
Synthesis simplicity:Scalable production is made possible by the cancer drug doxorubincin (DOX) into the reaction mixture, ZIF-8 NPs
simple and moderate synthetic conditions that may be used to easily with encapsulated DOX and PEG surface modification (DOX@ZIF-8/
produce MOFs-based composites. PEG) can be synthesized in one-pot (figure 1) [35].
Crystalline structure: MOFs-based composites may be character-
3.2. In situ generation in MOF cavities
ized by X-ray diffraction and designed with the aid of computational
models thanks to their clearly defined crystalline structure.
This method involves first diffusing precursors of the embedded
material into the MOF cavities, then in situ transforming the target ma-
3. Synthesis terials there. Here, the difficult issue is the production of the materials
utilized for modifications in the cavities of the MOFs rather than on
The properties and the performances of MOF-based composites are their surfaces, which may restrict the applications of this technology and
directly related to the MOFs structure, design and structure. For the also restrict the performance of the created MOF-based composites [36].
synthesis of MOF-based composites, there five roots could be used; (i) Nevertheless, there are still some issues with in situ generation. First
surface modified encapsulation, (ii) in situ generation in MOF’s cavities, off, the interior structures of MOF templates may be somewhat damaged
(iii) self-sacrificed template method, (iv) step-by-step construction of during the process of forming embedded materials. Additionally, it is
the sandwich-like heterostructure, and (v) one pot synthetic method. difficult to comprehend the structure-performance relationship of MOF-
based composites since it is difficult to manage the morphology, surface
3.1. Surface modified encapsulation
structure, and density of embedded elements.
The in situ generation method has produced NPs with pristine sur-
This technique also called “build-bottle-aroundship” and it is based
face topographies without modification with organic surfactants like
on two major steps: (i) preparation of well performed NPs with unique
CTAB and PVP. Additionally, NPs constrained by MOF cavities seemed
and uniform size, design, structure and morphology and then (ii) the
 28 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37

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Fig. 6. MOF properties and their applications in gas storage and separation.

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Fig. 5. Synthetic process of sandwiched MIL-101@Pt@MIL-101 composites is
shown in Fig. 5(a). (b and c) TEM pictures of the MIL-101(Fe)@Pt@MIL-101 in Reproduced with permission from Elservier [61].
their prepared state (Fe). (d) TEM images of the MIL-101(Cr)@Pt@MIL-101(Fe) controlled the thickness of the MOF shell in the nanoflower-like RhNi@
as prepared; (e) associated HAADF-STEM image; and (f) elemental mapping MOF-74(Ni) synthesis by tuning the Ni content in the self-sacrificed
images. Reproduced with permission from nature [48]. RhNi alloy template [41]. Additionally, we employed 2,5-dihydroxy-
relatively tiny and consistent in size, advantageous for real-world uses. terephthalic acid or 2-methylimidazole as etching agents to selectively
Surprisingly, under benign conditions, an in situ reaction in MOF cavi- dissolve Ni or Co components of RhCoNi ternary alloy NCs to create
ties serving as nanoreactors can easily produce NPs with certain unique MOF-74(Ni) and ZIF-67(Co) shells, respectively, on the alloy surface
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shapes and compositions. For instance, using a truncated octahedral [42]. The as-prepared composites appeared promise as adaptable plat-
inner cavity (diameter 2.5 nm) of a porous coordination cage (PCC-2) forms to comprehensively explore the relationship between performance
as the nanoreactor, Zhou et al. created uniform truncated octahedral of composites and structure of MOF shells due to the significant dispar-
face-centered-cubic (fcc) ruthenium (Ru) NPs with exposed 111 and 100 ities between the two obtained MOF shells in terms of aperture/cavi-
planes, which is frequently challenging [37]. ty size. Another metal source can be added while MOFs are still being
formed to create multicomponent MOF shells [43].
3.3. Self-sacrificed template method
The self-sacrificed template method was used to create several
Controlling the encapsulation status of embedded elements within MOF-based devices in sensor and catalysis applications in addition to
e-
the MOF matrix alone is crucial for MOF-based composites since it creating MOF-based composite nanoparticles [44]. By depositing a lay-
has a substantial impact on the practical performances, particularly in er of ZIF-CoZn thin film on a ZnOnanowire array using a self-sacrificed
catalysis and sensing. Although many different approaches to building template approach, for instance, the ZnO@ZIF-CoZn gas sensor was
well-defined NP@MOF composites have been tried, it can be difficult created. Foreign Co2+ was also engaged in the synthesis of ZnO@ZIF-
to identify generalized paths. The self-sacrificed template technique CoZn, in addition to the dissolved Zn2+ from the ZnO nanorod, which
resulted in the development of the dual metal MOF thin film on the ZnO
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works well for creating hollow or core-shell nanostructures because of

the characteristics of solid reaction and relatively slow kinetics [7,38]. nanowire array [45].
(d) A diagram of the coordination-assisted oxidative etching proce- The constructed ZnO@ZIF-CoZn core-sheath nanowire arrays ex-
dure and the related TEM images (scale bars represent 50 nm). Magni- hibit significantly improved performance in terms of selectivity, respon-
fied TEM pictures are insets (scale bars represent 5 nm). Reproduction siveness, recovery behavior, and working temperature.Reproduced with
permitted. Nature Publishing Group [40]. permission from wiley [45].
Finding the right template materials and reaction conditions is es- As a result, the self-sacrificed template method’s outstanding con-
sential for the successful fabrication of NPs@MOF composites using a trollability gives more room to construct various structured MOFs on
self-sacrificed template. The release rate of metal ions from the template the NP catalyst surface, permitting detailed investigation of the structur-
must match the coordination rate with organic linkers in order to ensure al-functional relationship in MOF-based composites.
the formation of the MOF shell on the self-sacrificed template surface 3.4. Step-by-step construction of the sandwich-like heterostructure
rather than in solution. Our team was the first to create metal oxide semi-
conductor@MOF composites using the self-sacrificed template method; As was already indicated, it can be difficult to limit the creation of
ZnO nanorods served as both a template and a source of Zn for the cre- functional materials inside or outside MOF matrices. Not only does the
ation of ZIF shells [39]. Both metal oxides and alloys containing transi- random distribution of functional NPs in the MOF matrix result in poor
tion metals can be used as template materials in the self-sacrificed tem- practical repeatability of MOF-based composites, but it also has a signif-
plate approach, which is straightforward and applicable to all materials icant impact on the investigation of the true structure-function connec-
[39,41].For instance, Wu and Li et al. effectively created PtNi@MOF-74 tion. Tang et al. created sandwich-like MOF-supported metal catalysts
composites using a coordination-assisted oxidative etching technique by to address this issue by growing additional MOF layers on top of the
using PtNi alloy NPs as a template [40]. catalysts [46,47].
The self-sacrificed template route has some limitations when it They first created MIL-101 that was loaded with Pt NPs, and then,
comes to template selection when compared to other approaches, but it around the already-made Pt@MIL-101 particles, they epitaxially devel-
provides a possible route to finely control the structure, thickness, and oped a new MIL-101 shell with a variable thickness [48]. Due to the
morphology of MOF shells. For example, the research team successfully fact that all Pt NPs were encapsulated in the incredibly thin MIL-101
 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37 29

now being conducted in both academic and professional settings. These

possible uses comprise:

4.1. Gas storage and separation

Gas separation and storage are strongly tied to many facets of hu-
man life, including energy use, industrial output, and environmental
protection. In particular, the separation of carbon dioxide is essential for
reducing the greenhouse effect, the storage of hydrogen and methane is
necessary for the widespread use of clean energy, and the separation and
storage of toxic gases like carbon monoxide and ammonia are crucial for
pollution control and the synthesis of industrial chemicals. An emerging
family of crystalline porous materials called metal-organic frameworks
(MOFs) are made of inorganic metal nodes and organic linkers, and re-
cently they have received a plenty of applications in this field [52,53].
The distinctive structural qualities of MOFs, such as high porosity, large

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surface area, tunable structure, and modifiable functionality, make them
particularly promising to be employed in gas storage and separation
Fig. 7. Modified UiO-66 as photocatalysts for boosting the carbon-neutral energy

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when compared to other porous materials [54,55].
cycle and solving environmental remediation issues. Reproduced with permission
In this context, researchers should concentrate more on highlighting
from Science direct [100].
the desired chemical properties of MOFs for required performance for
layer, substance diffusion was unaffected (Fig. 6). When hydrogenating
precise and effective seperation of the aforementioned energy-related
the C-O functional groups of a,b-unsaturated aldehydes, the resultant
gases, including CO2, H2, and CH4, and any additional harmful gases,
MIL-101@Pt@MIL-101 sandwich-like catalysts displayed remarkable
such as CO and NH3. Through careful regulation of pore size, great
selectivity. Be aware that the total catalytic efficiency of sandwich-like
progress has been made in the hydrocarbon separation of acetylene/eth-
heterostructures depends critically on the thickness of the outer MOF
ylene and propylene/propane [56,57].
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shell. Thick shells will impede reactant and product diffusions, signifi-
Additionally, using logically constructed MOFs, effective acetylene
cantly lowering the reaction conversion even though selectivity should
storage at ambient conditions was also accomplished [58]. MOFs out-
be increased to the same degree [47].
perform the majority of commonly used porous materials like zeolite
3.5. One-pot synthetic method and carbons in terms of specific surface area, which ranges from 1000
to 10,000 m2/g. MOFs, which have such a vast surface area, are thought
Each of the strategies discussed above requires a number of steps. to have tremendous potential for storing gases like H2 and CH4. The
In fact, a few instances showed how MOF-based composites might be key benefits of employing MOFs over conventional porous materials are
e-
made in a single step. For instance, Liu, Tang, and colleagues directly their consistent pore size and controllability of the entire structure. By
combined MOF-5 and Au precursors to create Au@MOF-5 [49]. The fine-tuning the size of the ligand, changing the functional groups on the
core-shell structures were produced by one-pot synthesis, where the Au ligand or metal sites, exchanging metal ions, or employing the coopera-
precursor was first converted to Au NPs by dimethyl formamide (DMF), tive regulation of ligands and metal sites, isoreticular chemistry within
and then MOF-5 spontaneously developed newly generated Au NP sur- MOFs makes it simple to obtain high H2, CO2, CH4, and C2H2 storage
faces. One-pot synthesis depends on controlling the development rate [59,60]. Recently, a number of start-up companies that make MOFs have
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of MOFs and/or the rate at which metal ions reduce. As a result, Luque flourished, advancing the field of employing MOFs for adsorption to a
and Li et al. were successful in controlling the encapsulation of “clean” new level. In light of this, this review article tries to summarize cur-
Pt clusters within UIO-66 by using a unique, kinetically controlled, one- rent advances in the use of MOFs for adsorption, both in the gaseous
step technique [50,51]. The use of a DMF solvent was crucial to the and liquid phases, while also incorporating the foundational knowledge
method’s success. In order to create Pt/UiO-66 composites, DMF and its needed to comprehend the adsorptive capabilities of MOFs. Adsorption
minor byproduct of oxidation (Me2NCOOH) would serve as a “bridge” applications with a list of the most promising structures and adsorption
to join MOF precursors to as-reduced Pt clusters, causing MOFs to de- mechanisms are given priority. At the conclusion of the article, a per-
velop anisotropically around the Pt surface. Although relatively straight- sonal perspective on the field’s future developments is offered. Although
forward and effective, one-pot synthesis is sadly not a widely used tactic. by no means comprehensive, this review tries to give readers a quick
A group of substances known as metal-organic frameworks (MOFs) are overview of the most recent developments in this field of study.
composed of metal ions or clusters joined by organic ligands. They are
4.2. Catalysis
highly porous materials with tunable properties that are appealing for a
variety of applications, including gas storage, separation, and catalysis.
In recent years, there has been a noticeable increase in interest in
Figure 6. Pt NPs are incorporated into MOFs using an in situ one-
catalytic chemistry [62]. Metal organic frameworks (MOFs), a family
step technique and an in situ one-step strategy with kinetic modulation
of porous materials, have generated a lot of interest recently due to their
(Fig. 7(a)). (b1-b4) TEM pictures of Pt@UiO-66 nanocomposites made
potential for use in catalysis [63-65].
using various H2/air volume ratios. A (b5 and b6) HAADF-STEM pic-
It is well recognized that the cyclization of propargylic alcohols with
ture of Pt@UiO-66 with the associated elemental mapping. Reproduced
CO2 is a significant industrial reaction, and noble-metal catalysts are
with permission from Wiley [51].
frequently used to achieve high product yields while maintaining en-
vironmental sustainability. For this reaction, a porous, noble-metal-free
4. Applications framework 1 with sizable, 1.66 nm-diameter 1D channels was created.
Compound 1 has high acid/base stability and can even last one month
Metal-organic frameworks (MOFs) are a relatively new class of ma- in corrosive triethylamine. Furthermore, the biological macromolecule
terials with a wide range of possible uses. As a result, research on them is ethisterone was an uncommon substrate for this MOF catalyst to exhibit
 30 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37

catalytic activity [66]. highest nonlinear R2 value (R2 = 0.9966) among the other isotherms.
In a separate study, compounds derived from manganese sulfide The highest amount of ARS that can be absorbed (qmax) is 979.0 mg/g.
(MnS) were synthesized and used for the first time to activate PMS The experimental results are consistent with the PSO kinetic model (R2
to break down the antibiotic levofloxacin (LVF) in water. In line with = 0.9702) [69]. In a separate study, Co- and Ni-MFU-4l, a family of
expectations, MnS significantly outperformed Mn2O3 in terms of LVF highly selective MOF catalysts for olefin upgrading, were the subject
degradation efficiency via PMS activation. The findings of quenching of in-depth X-ray absorption spectroscopy analyses that revealed the
studies, electro spin resonance identification, and electrochemical test- mechanisms underlying their deactivation. We further demonstrate that
ing showed that the primary mechanism in the -MnS/PMS system was Ni-CFA-1, a more practical and cost-effective substitute for Ni-MFU-4l,
electron transfer progress. Additionally, it was determined how different replicates both the latter’s excellent selectivity and local coordination
environmental factors affected LVF removal and the capacity of -MnS structure in the ethylene dimerization catalysis. Unmatched in activity,
to be reused, demonstrating the high application potential of the -MnS/ selectivity, and cost among heterogeneous ethylene dimerization cata-
PMS system. This study advances the fundamental understanding of lysts, Ni-CFA-1 activated by MMAO-12 reaches a turnover frequency
-MnS-mediated PMS activation and offers helpful details for the actual of 37100 per hour and a selectivity of 87.1% for 1-butene under ideal
use of manganese sulfide in water treatment [67]. circumstances. In a one-liter semibatch reactor, Ni-CFA-1 maintains its
Similar to this, another study revealed that copper- and calcium-based high activity for at least 12 hours, providing a path toward reliable and

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metal organic frameworks (MOFs) were successfully prepared and used scaleable MOFs for industrial catalysis [70].
as catalysts in the esterification and transesterification reactions for the Metal organic frameworks (MOFs) are unique design platforms for
manufacture of biodiesel from used cooking oil (WCO). The cubical biomimetic catalysts due to their varied chemical and physical prop-

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structure of MOFs with a crystallite size of 50 nm and thermal stability erties, but they have had only patchy success thus far due to the insta-
below 600 °C is indicated by catalyst characterization. The catalyst has bility of the MOFs used in physiological conditions. In this regard, the
undergone testing for conversion of WCO to biodiesel, and the biodiesel catalytic production of the bioactive compound nitric oxide (NO) from
samples meet ASTM requirements. The catalyst loading (X1), reaction endogenous sources, S-nitrosothiols, is demonstrated using Cu(II)1,3,5-
temperature (X2), and alcohol-oil ratio (X3) are further process param- Benzene-tris-triazole (CuBTTri) (RSNOs). The CuBTTri-poly material
eters that are improved using response surface methodology (RSM) via retains its catalytic function for the production of NO once it has been
central composite design (CCD). To examine the dynamic interaction prepared, with tunable release kinetics proportional to the total amount
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between process factors and biodiesel yield (YBD%), the second-order of CuBTTri embedded into the polymeric material and a surface flux
regression model is used. With the catalyst loading set at 1.0 g/100 mL, corresponding to the therapeutic range of 1-100 nm cm2 min1. This
the reaction temperature at 60 °C, the alcohol-to-oil ratio at 20, and the function is maintained even after exposure to blood [71].
biodiesel production at 84.5 (vol%), the ideal process parameters have
4.3. Sensing
been identified. The proportion of difference between experimental and
projected outcomes is less than 5%, indicating good agreement. For
The majority of modern sensing techniques rely on chromatography,
three cycles, the regenerated catalyst significantly reduces the biodiesel
including gas chromatography-mass spectrometry, liquid chromatog-
production by up to 7% [68].
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raphy-tandem mass spectrometry, and high-performance liquid chro-
By adding sulfamic acid to the zeolitic imidazolate framework (ZIF-
matography, as well as fluorometry, colorimetry, enzyme biosensors,
90), an effective bifunctional catalyst with synergetic Lewis and Brnsted
and electrochemical methods [72-78]. These evaluation methods have
acid sites was created in order to increase the acidic sites in catalysts
a number of drawbacks, including time-consuming sample processing,
to increase the conversion efficiency of microalgal lipids into biodiesel
expensive equipment, toxic chemicals, and expensive time-cost. There-
(SA). It increased the amount of Brnsted and Lewis acid sites when the
fore, there is an urgent need for the expansion of an efficient method
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sulfamic acid that joined with ZIF-90 through the imine bond (C N)
for determining various analytes that is accurate, easy, and time-saving
delivered protons and disrupted coordinated Zn-N bonds in ZIF-90. The
[78,79]. Due to Metal-organic frameworks (MOFs) substantial thermal
ratio of Brnsted acid to Lewis acid increased from 0.32 to 0.49, while
stability, high porosity, and huge surface areas, they have been used as
the overall acidity of the ideal catalyst increased from 0.478 to 0.848
detecting platforms for special analytes such as anions, cations, gases,
mmol/g. While Brnsted acid sites in bifunctional catalysts were more
organic small molecules, explosives, temperature, humidity, and pH,
active in esterification reactions of free fatty acids, Lewis acid sites were
based on the eximious sorption kinetics, reversibility, and guest-induced
more active in transesterification reactions of triglycerides in microal-
changes in their structure and/or characteristics [80]. These features
gal lipids. The result was that the best catalyst increased the conversion
make MOFs a promising candidate for sensitive and selective sensors in
efficiency of microalgal lipids into biodiesel from 80.6% to 98.3% at
environmental and industrial applications.
200 °C, while conversion efficiency remained 91.7% after 6 reusability
The focus is on optical MOFs because of their aromatic sub-units.
cycles. The weight ratio of SA to ZIF-90 was 0.05 [69].
Since aromatic linkers emit light [81], many MOFs have been discov-
A calcium-terephthalate metal-organic framework ([Ca(BDC)
ered to be photoluminescent. The other type of MOF sensors are based
(H2O)3]) was synthesized in a study using recovered terephthalic acid
on the powerful photoluminescence characteristics of lanthanide ions
from waste polyethylene terephthalate (PET) as a precursor. Its ability
(Ln3+), which undergo luminescence variations [82] [83]. Due to the
to adsorb dye Alizarin red S (ARS) from an aqueous solution was exam-
numerous 4f-4f transitions of the lanthanide centers and the clearly de-
ined for the first time. We looked into effective variables including pH,
fined porosity of the frameworks, lanthanide MOFs, for instance, are
adsorbent dose (m), and starting ARS concentration (C). A proper rela-
discovered to be the ideal option for creating new fluorescence sensors
tionship between the effective variables and either the removal percent
[84]. Ln-doped MOF composites offer a novel class of fluorescence sen-
(R%) or adsorption capacity (q) response was produced by BBD with
sor for this purpose, which can detect gases, cations, anions, organic
15 runs. For the following ideal conditions: pH = 6, m = 2 mg, and C
small molecules, humidity, temperature, and pH [85].
= 379 mg/L, the suggested BBD model produced a maximum removal
By modifying the electrode surface with various hybrid materials
percentage (R% = 69.97) and adsorption capacity (q = 788.3 mg/g) of
(such as functionalized graphene, preanodized/mediator-modified car-
ARS. A Taguchi design with nine runs produced the best results at pH
bon substrates, and Au-based nanomaterials), it is possible to design
= 5, m = 2, and C = 300 mgL-1. The Langmuir-Freundlich isotherm
new electrochemical sensors or biosensors with desirable analytical and
model well captures the adsorbent-adsorbate behavior since it has the
 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37 31

electrochemical features to use for standard environmental sensing or filler to create MOF-based PMMs [99]. They did this by managing the
biosensing systems [86]. Selecting appropriate materials to combine internal concentration polarization (i.e., using lower structural parameter
with the frameworks may be able to overcome the MOFs’ large empty values).
volume limitation on conductivity [28]. The degree of internal concentration polarization is frequently as-
In order to overcome this obstacle and serve as effective electro- sessed using the structural parameter. Phase-in-version was used to
chemical sensors for environmental and biological targets, various MOF create porous matrix sub- strates with three distinct types of MOFs by
composite-based platforms have been created [87]. On the other hand, combining MOF particles with a polyacrylonitrile doping solution. The
due to their exceptional physicochemical features, noble-metal nanopar- growth of comparatively large macropores inside the PMMs, which in-
ticles (NPs) (such as Au, Ag, Pd, and Pt) can be anticipated in sensing, creased the mass (water/solute) transfer effectiveness inside the PMM
imaging, cancer therapy, optical data storage, and catalysis. However, substrate, was the cause of the improved FO performance. Liu et al.
because of their high surface energy, aggregation limits the aforemen- created self-standing dense and homogenous UiO-66 nanocomposite
tioned performances. In order to overcome this difficulty using numer- thin films (about 400 nm) integrated into polysulfone containing sulfon-
ous strategies, the researcher mixes them with MOFs. The resulting ic functional groups using a straightforward solution casting process and
composites may be an excellent sensor for different chemical recogni- solvent evaporation [100].
tion [88,89]. It has been widely documented that post-synthesis swapping or

f
In conclusion, MOF nanocomposites have been exploited for tem- strengthening of UiO-66 in various noncovalent bonding forms enhanc-
perature sensing as well as the detection of a number of significant an- es interfacial interaction with polymers [101,102]. In particular, during
alytes, including heavy metal ions, anions, aromatic hydrocarbons, and the thin-film deposition process, interfacial binding between UiO-66 and

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hazardous phenolic chemicals. We believe that the knowledge presented the sulfonated polysulfone might develop in thin films in situ. Because
in this review about the creation and use of MOF nanocomposites as of its enhanced compatibility, the UiO-66, a zirconium-based MOF has
photoelectrochemical sensors will aid the research teams in develop- a conformational reduced flexibility and backbones, increasing the me-
ing and establishing more sophisticated MOF-based sensing strategies. chanical and structural qualities of thin films strength [92].
However, additional work needs to be done to enhance the MOF nano-
4.5. Pharmaceuticals and Biotechnology
composites’ sensing capabilities, particularly with regard to size, shape,
design, and the functionalization of MOFs with many molecules by
It is crucial to take into account a material’s function and biocom-
Pr
post-synthesis/dopant alterations and entrapment. Functionalized MOFs
patibility when using it in biomedical applications, especially those that
may also aid in the development of sensitive and selective sensors.
take place in vivo. Some of the current MOFs might worry about the
4.4. Water treatment and purification potential leaching of harmful metal ions or other components in their
structure [103,104]. However, a couple of intriguing porous crystals
Numerous methods for the preparation of MOF-based membranes MOFs were used as nontoxic medication delivery systems [105].
have been developed since the introduction of MOFs to membranes in a They must be built from components that are physiologically and
variety of industries to improve their overall performance [90,91]. ecologically acceptable for a variety of purposes. For instance, harmless
e-
These methods have been applied to enhance the design of MOF- MOFs were obviously preferred over hazardous ones in the majority of
based membranes for liquid separation, especially in the desalination biological applications, such as drug delivery systems or intracellular
sector employing capacitive deionization [92], adsorption desalina- imaging. Recently, researchers looked into the antibacterial activity of
tion [93], and membrane distillation [94], among others. Accurate and MOFs based on nontoxic antimicrobial cations [106,107]. Zinc-based
quick water purification depends on the proper design of MOF-based MOFs are being introduced into bioapplication domains, especially as
membrane manufacturing techniques. The development of preparation drug carriers, due to the low toxicity of zinc ions. Combining sever-
Pr

procedures, which have a substantial impact on the configuration of al antibiotic medications and materials allowed researchers to quantify
MOF-based membranes and their strength and removal effectiveness, the antibacterial activity [106]. In reality, dermatologists frequently uti-
is a significant determinant of the performance of MOF-based FO, RO, lized zinc, an endogenous low-toxic transition metal, as a cicatrizing
NF, and UF membranes in water treatment [92,95]. agent, a skin moisturizer, and a combination of anti-dandruff, astringent,
Although the fundamentals were established in the 1960s, the FO anti-inflammatory, and antibacterial agents [108,109]. Zn2 is typically
method has lately gained popularity for a variety of applications, most employed as a connecting point in nonlinear optically active MOFs to
notably saltwater desalination [96]. For application in the water sector, prevent undesirable d-d transitions in the visible region.
scientists and engineers have looked for innovative methods for creating Recent research (Kitagawa et al. 2004; Rezwan et al. 2006; Ye et
FO membranes. Although several porous matrix membranes (PMMs) al. 2015) have highlighted the potential biological and medical applica-
have been employed for NF and UF membranes [91], FO- TFN mem- tions of Zn-based MOFs as useful drug delivery vehicles and nontoxic/
branes are less frequently used because of their structural resemblance biocompatible medicinal agents [110,111]. Drugs could be encapsulated
to porous asymmetric membranes. by MOFs and released gradually through their pores [112]. The thera-
For FO applications, it is required to develop a very stable, active, peutic molecule was inserted directly as an organic constituent of the
and dense layer on the membrane’s top surface in order to get over this MOF framework in biocompatible drug carriers to prevent side effects
restriction. By modifying the conventional dense film-casting method, [108,113]. Zinc-based MOFs with the aforementioned characteristics,
Arjmandi et al. created a thin-film PMM mixed with magnetic water-un- together with low toxicity, biodegradability, and diverse functionality,
stable MOFs ((magnetic) ZnO@MOF-5) that significantly improved the can be thought of as excellent candidates for creating nanoencapsula-
performance of the FO process [97]. In a different work, a TFN membrane tors and achieving controlled drug release using cutting-edge delivery
with a suitable 2D MOF (copper 1,4-benzenedicarboxylate) nano-filter methods. According to Bahrani et al., [108], the benign metal Zn and
in a polyamide active layer was created to improve water flux and anti- low toxicity linkers carboxylate or phetalat were used to build up the
fouling capability without reducing selectivity for FO applications [98]. available porosities in these materials.
Controlling the internal concentration polarization is essential for en- The nature of host-guest interactions and pore properties have a sig-
hancing FO performance. In order to improve the mass transfer effi- nificant impact on how well drug delivery systems operate in physiolog-
ciency in FO support substrates, Lee et al. used MOFs as a detachable ical media [114,114].
 32 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37

Deferiprone treatment for hemosiderosis can be seen as a promising native to lessen their negative effects on human health. In order to purge
ligand in bioactive Zn-based MOFs, as revealed by Burrows et al. [116]. organic pollutants, innovative adsorbents and photocatalysts have been
Deferiprone as a chelating agent may be contained in the MOF’s tri- developed using these coordination polymers [127]. The most recent re-
zinc secondary structure before being released into the PBS. As shown ports on MOFs for wastewater treatment, which are mainly concerned
by Sun et al. [117], the stiff scaffold provided by the bidentate carbene with the elimination of organic contaminants, have been provided in the
ligand makes Zn-MOF an effective carrier for the release of cisplatin, subsections that follow. The efficacy of MOF-based photocatalysts for
an effective anticancer agent with in vitro cytotoxic effects for ovari- the degradation of organic colors, medicinal medicines, insecticides, and
an cancer cells A2780. This MOF’s structure is based on the bridging phenolic compounds is extremely investigated [128,129]. MIL-53(Fe)
and chelating ligands 1,4-diazabi-cyclo [2.2.2] octane (DBCO) and was reported by Xiang et al. (2017) for the removal of carbamazepine
1,4-benzenedicarboxylic acid (H2bdc), respectively. By using the MTT and clofibric acid from deionized water, sewage treatment plants, and
assay, the IC50 value and cytotoxicity of MOF for human hepatoma cell river water. Inhibiting metabolism, reproduction, and embryonic devel-
(HuH7) were found to be 1.0 mg/mL [108]. opment, these substances are medications used to treat excessive blood
cholesterol levels and epilepsy, respectively. In 270 minutes, the met-
4.6. Environmental remediation
al-organic framework (MOF)/H2O2/visible system decomposed clofibric
acid and carbamazepine, respectively, in 98.2 and 90.1% (deionized
For the removal of heavy metals and contaminants from soil and air,

f
water), 94 and 88% (river water), and 71 and 86% (municipal waste-
MOFs have been proposed. In accordance with the World Water Devel-
water) [130]. In addition to delayed kinetics and the need for a very low
opment Report 2020, 1.6 billion people do not have access to clean wa-
operational pH of 3, the process produced by-products that resembled

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ter [118]. Additionally, the inclusion of extremely harmful compounds
humic acid and fulvic acid and needed extra treatment to be completely
is fast lowering the quality of water supplies. Hazardous substances like
removed from water [130].
dyes, insecticides, phenolics, and chlorinated chemicals are released due
The in situ production of reactive species (OH, O2-), which are ca-
to anthropogenic activities like agriculture and industry.
pable of mineralizing phenolic pollutants even at low concentrations,
In addition, routine activities have been introducing new pollut-
could be accomplished by heterogeneous photocatalysts using solar en-
ants such medications, personal care items, and hormone disrupt-
ergy [131].
ing substances in minute amounts. The ecosystem may be serious-
The use of metal-organic frameworks (MOFs) as photocatalysts for
ly threatened by these harmful and cancer-causing micropollutants
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the degradation of pollutants was first proposed by Garcia’s research
[119,120]. The rising need for fossil fuels like coal, oil, and natural
team [132]. The metal ions in the scaffold are assumed to be respon-
gas is linked to another top-priority environmental concern. Uncon-
sible for the photocatalytic activity, while the organic linkers operate
trolled burning of fossil fuels results in the release of harmful and
as light-absorbing chromophores that can gather photons from a wide
offensive gases, such as volatile organic compounds and volatile sul-
range of the solar spectrum. When comparing the moles of phenol de-
fur-organic compounds, as well as COx, NOx, and SOx. These gases
stroyed per metal ion in the material, MOF-5 displayed comparable pho-
cause the air quality to significantly deteriorate and are either direct-
tocatalytic activity to commercial TiO2 P25 and ZnO [133].
ly or indirectly related to acid rain and global warming [121,122].
e-
Heterogeneous photocatalysis is a successful method for removing or-
ganic pollutants, and semiconductors like TiO2, ZnO, and ZnS continue 5. Conclusion and Future Prospects
to be the most widely used options. Due to their wide band gap energy
(Eg * 3.2–3.7 eV) and poor material recovery, these photocatalysts have Significant progress has been made in the introduction of MOFs as
some important limitations, including limited solar activity [123-125]. effective catalysts for gas separation, medical needs, and as remediation
As several 3d-block transition metals’ oxides and sulfides are known agents for pollution.
Pr

to have small bandgap energies (1.11 eV for CoFe2O4), they can be used The enormous porosity and tunable structure of MOFs enable heavy
to capture the complete UV-visible spectrum of the sun (Gupta et al. loadings of biological molecules. But important factors including sta-
2020c). As photocatalysts, MOFs with the metal centers Zn(II), Cu(I)/ bility, toxicity, and biocompatibility may limit MOFs’ performance in
Cu(II), Co(II)/Co(III), and Fe(II)/Fe(III) enable the degradation of or- biomedical applications.
ganic pollutants under UV/visible light. By transferring charge from the The antibacterial activity and biocompatibility of MOFs can be im-
ligand to the metal cluster, the organic linkers in the MOF structure can proved, making them a suitable material for medical devices that might
serve as light “receptionists,” activating the transition metal centers. greatly enhance healthcare features.
In photo-redox reactions, the excited MOF can generate elec- Describe how MOFs can be functionalized and modified with oth-
tron-hole pairs that can be transported to the surface. The poor coordi- er nanomaterials to improve their separation capabilities, increase their
nation of d-block transition metals with ligands in MOFs facilitates the sensitivity, and improve their selectivity when utilized in sensing appli-
formation of coordination vacancies where the coordinatively unsatu- cations.
rated metal centers act as Lewis acid catalytic sites [126]. Moreover, The unique property of MOFs, when compared to other cutting-edge
conjugated organic linkers could be used to adjust the light-harvesting materials, is that their separation performances are unaffected by the
characteristics of these coordinated polymers. The MOFs are regarded presence of moisture, strongly indicating their potential for use in practi-
as the next generation of photocatalysts since they can utilize the full cal industrial applications such as water desalination, water purification,
solar spectrum. Since gas collection and storage was one of MOFs’ ini- and gas storage.
tial uses, it is possible to employ MOFs as adsor- bents or catalysts to These MOF adsorbents are predicted to play a significant role in the
remove harmful gases, which could prove to be an efficient and direct field of CO2 capture if enhanced, as their high stability will improve
method of reducing the rising level of air pollution. their resistance to minor components (SOx and NOx) in flue gas as well
On the other hand, municipal and industrial wastewaters are dis- as decreases in their regeneration energies and enormous synthesis costs.
posed of directly into pure water sources without any preparation, there- The availability, affordability, kinetics of toxic gas adsorption/
by introducing a variety of harmful organic compounds. By collecting desorption, reusability, and long-term stability of MOFs toward such
and decomposing these contaminants into non-toxic chemicals, met- corrosive gases are significant practical challenges that need to be ad-
al-organic frameworks (MOFs) are gaining attention as a viable alter- dressed.
 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37 33

Researchers have created these MOF-based catalysts that work in- ly overlooked in these research studies. It is difficult to evaluate and
credibly well in polymerization reactions by utilizing their intrinsic po- compare the cost-to-performance ratio with other traditional materials
rosity and the ability to synthesize them to create single-site catalysts because there is no reliable estimate of the manufacturing cost of MOF.
with clearly defined structural properties. The least hazardous transition metals, including Fe and Zn, can
Due to their relative young within this sub-field, these MOF polym- be given priority, even though it is not possible to limit the amount of
erization catalyst materials have not yet achieved commercialization and organic linkers used in MOF production. Furthermore, by using sol-
use in industrial processes; nonetheless, MOF materials have in general vent-free synthesis, hazardous solvents can be completely eliminated.
achieved commercialisation. Given the recent commercial success of Following alternative solvent-free routes could lower the cost of pro-
MOF materials, their potential application has a promising future be- duction because the synthesis of MOF through solvent-free methods
cause they can compete in activity and selectivity with present industrial like liquid-assisted grinding and aqueous synthesis is comparably less
catalysts. expensive ($13-36 kg-1) than organic solvent (solvothermal) synthesis
Future research should examine how the MOF catalyst’s physical ($35-71 kg-1) (DeSantis et al. 2017).
characteristics vary and what impact those variations have on chemical The practical application of MOFs necessitates a thorough compre-
synthesis of the MOF-based composites using in-situ techniques such as hension of the chemical pathways and their applicability in actual waste-
IR spectroscopy, Raman, X-ray absorption and so on. water, both of which should be thoroughly investigated before making

f
In the near future, it is strongly advised to understand the catalytic any generalizations about their applicability in wastewater treatment
mechanism of MOFs in order to have a clear understanding of how to facilities.
optimize the reaction parameters and conditions for improved perfor- It is difficult to compare the benefits of adsorption versus catalysis,

oo
mance in chemical synthesis, including sepration, polymerixation, and despite the fact that a small number of papers are devoted to analyzing
biofuel production. the reusability difficulties.
MOFs frequently have drawbacks that restrict their use, such as weak MOFs are adaptable catalysts for air purification because they can
mechanical strength, poor stability, and a single function. Depending on selectively catalyze the reduction of NO with NH 3 or thermally de-
the intended application, combining MOFs with particular materials is grade volatile organic sulfur compounds to produce S 8. Even though
strongly advised. MOFs have several advantages for removing gaseous pollutants, they
The oxidation of functional groups or metal nodes during the synthe- are thermally unstable and start to break down at temperatures as low
Pr
sis processes, which can both result in the collapse of the micropores, as 300–400 °C. The thermal stability of MOFs can be improved by in-
may cause MOF structures to deteriorate after the compounding pro- creasing the coordination forces with a proper choice of organic linkers
cess. Such problems may be resolved, at the very least, by optimizing and metal nodes.
the synthesis settings and conditions or utilizing eco-friendly synthesis Additionally, the hydrophilic nature of MOF metal nodes, particular-
techniques. ly those that contain transition metals, reduces the active site density and
Additionally, the maximum loading of metal ions in emerging mois- jeopardizes structural integrity through hydrolysis processes. By select-
ture filtering and ion exchange techniques limits the number of NPs in ing hydrophobic linkers and grafting oleophilic functions onto the open
MOF composites. The amount of metal ions loaded for initial wetness metal sites, it is possible to create hydrophobic MOFs that will perform
e-
filtering depends on the solubility of the precursors in solution and the better by preventing the entry of water molecules.
duration spent immersing the MOF powders, while the maximal loading Additionally, the MOF stability should be assessed by preserving
for an ion-exchange method is determined by the number of active sites MOFs in various atmospheric settings to observe how MOFs degrade in
in MOFs. As a result, one of the primary difficulties in the synthesis the presence of atmospheric oxygen (Du et al. 2019).
of metal NP/MOF composites is to increase the metalNP loading while Overall, it appears that military applications will more likely lead to
Pr

preventing their simultaneous aggregation in MOFs. MOF commercialization than civilian ones. Every conceivable premise
The production of high-quality MOF-based composites depends on for the commercialization of MOFs is based on their low cost of pro-
the size, dispersion, and interactions of the MOF particles in the matrix. duction, great efficacy, and lack of dependence on secondary chemicals
The capacity of the membranes to separate will be enhanced by the or processes. Therefore, finding inexpensive precursors is crucial for an
great homogeneity and dispersion of MOF particles. As a result, there efficient way to manufacture MOF.
is a considerable demand for MOF particles with surface functional- A cost-saving solution could be to locate the least-costly way to pro-
ization and size tuning. However, this research is still in its infancy, so duce a MOF instead of using a multi-step procedure.
more work needs to be done in the future. The synthesized MOF com- Another persuasive argument against using MOFs in the wastewater
posites exhibit improved gas absorption, separation, storage capability, treatment process might be made by doing a more thorough assessment
and catalytic capabilities thanks to the combination of MOFs and other of MOF toxicity to people and other living things. Although the current
functional species. Additionally, the interaction of functional elements development of MOFs for environmental applications is constrained by
and matrix materials with MOF structures can expand the uses of MOF a lack of understanding, MOFs’ future importance is very certain. We
composites in new industries including fuel cells, electrical catalysis, predict that transition metal-based MOFs will replace current adsorbents
and drug delivery and release. and catalysts in commercial air and gas decontamination operations in
Though it has been asserted that MOFs are stable over a large pH the next years.
range, there aren’t many instances of this, therefore it’s impossible to The ability of the synthesis method to be scaled up from an academ-
generalize and apply this to all MOFs. Along with the reusability, their ic/laboratory setting to a big industrial one will determine the future of
durability against oxidants and radiation sources must also be taken into MOFs. The different factors that should be considered while developing
consideration. industrial MOF production processes include cost, raw material avail-
A barrier to the commercialization of synthesized nanoscale MOF ability, technical simplicity, yields, purity and quality of synthesized
crystals for wastewater treatment may be the use of hazardous heavy MOFs, and environmental impact. The space-time yield of the synthesis
metals (Cd, Cr, and Co), organic linkers (4,4-bipyridine and trimesic reaction is frequently used to assess the effectiveness of a selected ap-
acid), solvents (N N-dimethylformamide, chloroform, and acetone), and proach. The mass of a MOF produced in one day of synthesis, expressed
potential toxicity of the crystals (Kumar et al. 2019). in kilograms per cubic meter of the reaction mixture, is known as the
The price of manufacturing MOFs is another topic that is frequent- space-time yield.
 34 H. Meskher et al. / Journal of Composites and Compounds 5 (2023) 25-37

For producing MOFs on a wide scale, techniques with high space- [13] H. Meskher, S.B. Belhaouari, K. Deshmukh, C.M. Hussain, F. Sharifianjazi, A
time yield values are thought to be the most effective. The literature Magnetite Composite of Molecularly Imprinted Polymer and Reduced Graphene
Oxide for Sensitive and Selective Electrochemical Detection of Catechol in Water
has discussed the space-time yield values of popular MOFs synthesized
and Milk Samples: An Artificial Neural Network (ANN) Application, Journal of
utilizing various procedures (Rubio-Martinez et al. 2017). For environ-
The Electrochemical Society 170(4) (2023) 047502.
mental applications, it makes little sense to produce materials with a [14] H. Meskher, F. Achi, F.B. Moussa, A. Henni, H. Belkhelfa, A Novel Pen-
high environmental imprint. Because of this, before commercializing tachlorophenol Electrochemical Sensor Based on Nickel-Cobalt Layered Double
the process, factors like environmental footprint should be taken into Hydroxide Doped with Reduced Graphene Oxide Composite, ECS Advances 2(1)
account in addition to variables like space-time yield. (2023) 016503.
Commercial MOFs made by Badische Anilin und Soda Fabrik, MOF [15] B. Wang, Z. Zhang, F. Yuan, D. Zhang, Q. Wang, W. Li, Z. Li, Y.A. Wu,
W. Wang, An insight into the initial Coulombic efficiency of carbon-based anode
Apps, and MOF Technologies, including HKUST-1, MOF-5, UiO-66
materials for potassium-ion batteries, Chemical Engineering Journal 428 (2022)
series, ZIF-67, and ZIF-8, are offered by Sigma-Aldrich (Rubio-Marti-
131093.
nez et al. 2017). [16] A. Zuliani, N. Khiar, C. Carrillo-Carrión, Recent progress of metal–organic
The main barrier keeping MOFs from displacing traditional adsor- frameworks as sensors in (bio)analytical fields: towards real-world applications,
bents in environmental applications is their high cost as of yet. But as Analytical and Bioanalytical Chemistry 415(11) (2023) 2005-2023.
the industry develops, new players are joining the market to sell less [17] Q. Wang, G. Yang, Y. Fu, N. Li, D. Hao, S. Ma, Nanospace Engineering of
Metal-Organic Frameworks for Heterogeneous Catalysis, ChemNanoMat 8(1)

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well-known MOFs, and they’ll undoubtedly offer MOFs up to their use
(2022) e202100396.
in practical environmental applications.
[18] H. Meskher, S.B. Belhaouari, K. Deshmukh, C.M. Hussain, F.J.J.o.T.E.S.

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Acknowledgment Sharifianjazi, A Magnetite Composite of Molecularly Imprinted Polymer and Re-
duced Graphene Oxide for Sensitive and Selective Electrochemical Detection of
Catechol in Water and Milk Samples: An Artificial Neural Network (ANN) Appli-
The authors received no financial support for the research, au-
cation, 170(4) (2023) 047502.
thor-ship and/or publication of this article.
[19] L. Bazli, M. Bazli, A review on the mechanical properties of synthetic and nat-
Conflicts of interest ural fiber-reinforced polymer composites and their application in the transportation
industry, Journal of Composites and Compounds 3(9) (2021) 262-274.
[20] Y. Deng, Y. Wang, X. Xiao, B.J. Saucedo, Z. Zhu, M. Xie, X. Xu, K. Yao, Y.
All authors declare no conflicts of interest in this paper.
Zhai, Z. Zhang, J. Chen, Progress in Hybridization of Covalent Organic Frame-
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works and Metal–Organic Frameworks, Small 18(38) (2022) 2202928.
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