Recent Advances in Metal Organic Frameworks-Based Magnetic Nanomaterials For Waste Water Treatment

Environmental Science and Pollution Research
https://doi.org/10.1007/s11356-023-31162-8
REVIEW ARTICLE
Recent advances in metal organic frameworks–based magnetic

nanomaterials for waste water treatment
Shwetharani Ramu1 · Itika Kainthla2 · Lavanya Chandrappa1 · Jyothi Mannekote Shivanna3 · Brijesh Kumaran4 ·
R. Geetha Balakrishna1
Received: 31 May 2023 / Accepted: 17 November 2023

© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023
Abstract
Magnetic nanoparticle–incorporated metal organic frameworks (MOF) are potential composites for various applications such
as catalysis, water treatment, drug delivery, gas storage, chemical sensing, and heavy metal ion removal. MOFs exhibits high
porosity and flexibility enabling guest species like heavy metal ions to diffuse into bulk structure. Additionally, shape and
size of the pores contribute to selectivity of the guest materials. Incorporation of magnetic materials allows easy collection
of adsorbent materials from solution system making the process simple and cost-effective. In view of the above advantages in
the present review article, we are discussing recent advances of different magnetic material–incorporated MOF (Mg-MOF)
composite for application in photocatalytic degradation of dyes and toxic chemicals, adsorption of organic compounds,
adsorption of heavy metal ions, and adsorption of dyes. The review initially discusses on properties of Mg-MOF, different
synthesis techniques such as mechanochemical, sonochemical (ultrasound) synthesis, slow evaporation and diffusion meth-
ods, solvo(hydro)-thermal and iono-thermal method, microwave-assisted method, microemulsion method post-synthetic
modification template strategies and followed by application in waste water treatment.
Keywords Magnetic nanoparticles · MOF · Fe · Water treatment · Adsorption · Degradation
Introduction environment is critical for ensuring a healthy and sustain-

able future for all beings. It is a critical global challenge that
The ever-increasing human population and efforts to meet requires collective and sustained action in environmental
their needs have extensively damaged the ecology. Envi- protection efforts (Kumar et al. 2022). Water quality and
ronmental deterioration is one of the early signs of anthro- scarcity have been recognized as one of the major crises of
pogenic activity and includes factors like industrialization the twenty-first century. The global water crisis involves the
and its accompanying negative repercussions. Protecting the increasing insufficiency of clean and safe water for drinking,
irrigation, and other uses. It has become the major issues of
concern which requires ardent efforts in water management
Responsible Editor: Angeles Blanco for sustainability (Jury &Vaux Jr 2007). The priority is to
take important steps to reduce water pollution in order to
* R. Geetha Balakrishna protect human health, preserve aquatic life, and ensure a
[email protected]
sustainable water future (Abdelhameed et al. 2023a, 2022,
1
Centre for Nano and Material Sciences, Jain (Deemed-to-Be 2023b; El-Shahat et al. 2020; Emam et al. 2021). On the
University), Jain Global Campus, Kanakapura, Bangalore, other hand, water remediation is the process of removing
Karnataka 562112, India pollutants from water to make it safe for drinking, irriga-
2
School of Physics and Material Sciences, Shoolini tion, and other uses. The need for water remediation arises
University, Bajhol, Solan, Himachal Pradesh 173229, India from the widespread contamination of water sources due
3
Department of Chemistry, AMC Engineering College, to a variety of anthropogenic factors involving release of
Bannerughatta Road, Bengaluru, Karnataka 560083, India both organic and inorganic pollutants into the water streams
4
Department of Sustainable Energy Engineering, Indian (Ghasemzadeh et al. 2014, Lu &Astruc 2020, Mishra
Institute of Technology Kanpur, Kalyanpur, Kanpur, et al. 2020). Therefore, investment in water remediation
Uttar Pradesh 208016, India
13
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technologies and practices is necessary to address the decades. MOFs have enormous porosity and customizable
impacts of water pollution. Due to the significance of organic pore diameters compared to typical adsorbents, enabling
compounds and their versatile industrial use, their efficient extremely selective adsorption of dangerous pollutants from
removal from wastewater has become a serious issue. The the environment (Abdelhameed et al. 2016; Dhaka et al.
majority of organic compounds particularly, dyes have haz- 2019; Liu et al. 2022; Wang et al. 2020). These materials,
ardous aromatic molecular structures that are stable and however, are challenging to recycle from the mixed solution,
chemically inert to natural degradation processes like micro- whereas magnetic materials are one of the most desirable
bial breakdown. Sadly, a lot of dyes are extremely poison- materials used in water remediation but face various chal-
ous and even at low concentrations can have mutagenic or lenges with their stability due to high surface energies and
cancerous effects on aquatic life and people. Thus, it is now a low surface area. Thus, by combining MOFs with magnetic
problem for the environment on a global scale to effectively particles overcomes the individual limitations of the two
remove these dyes from water solutions (Boulkhessaim et al. materials. Also, attained magnetism is one of the numerous
2022, Lu &Astruc 2020, Okoro et al. 2022, Pi et al. 2018, characteristics of MOFs; it can be easily achieved by add-
Tchinsa et al. 2021). On the other hand, various inorganic ing magnetic moment carriers such as open-shell organic
pollutants such as heavy metal ions in water are another ligands or paramagnetic metals. The magnetic MOFs exhibit
major contributor to have drawn researcher’s attention. Some higher specific surface area and more surface active sites
examples of inorganic substances include radioactive com- in addition to easy recovery by external magnetic field in
pounds, heavy metals, halides, oxyanions, and cations. Due comparison to non-magnetic MOFs. Most magnetic MOFs
to their extended half-lives and lack of biodegradability, to date contain paramagnetic metal centres, especially the
they could linger longer in aquatic systems and worsen the first row of transition metals typically, V, Cr, Mn, Fe, Co,
water quality. The accumulation of heavy metals and other Ni, and Cu. Both the spin quantum number and magnetic
anionic pollutants like arsenic, nitrates, and fluorides leads anisotropy can be changed in these metals, which can exist
to significant diseases after prolonged ingestion (Boix et al. in various oxidation states. In a field without boundaries,
2020; Isaeva et al. 2021; Kobielska et al. 2018). Tackling the potential for such a wide range of variables opens many
the global water crisis requires a multi-faceted approach scopes for applications, and owing to their versatility, these
that includes efforts from passionate research and innova- magnetic-based MOFs are commonly employed for water
tions. In response to calls for sustainable and environmen- treatment applications. Furthermore, the fact that they have a
tally friendly approaches, research trends in the latter half stiff, crystalline structure made of organic linkers that allows
of this decade are focused on green engineering, the design for the possibility of permanent porosity and post-synthetic
and implementation of procedures that reduce pollution chemical alteration of the inorganic and organic components
and support environmental sustainability without sacrific- increases their utility. Other than its structural efficiency, the
ing quality and efficiency. Several technologies, including MOF-based magnetic nanoparticles are easily recycled from
ion exchange, biological treatment, chemical precipitation, the reaction media by an external magnetic field, which has
and reverse osmosis, have been developed for water purifica- attracted many researchers particularly for the purification of
tion. Even though these approaches are efficient, their poor the water. Thus, problems such as the generation of second-
selectivity and high cost typically make them impractical ary pollution or difficulty in separation can be avoided, and
for most applications (Peng et al. 2022; Rego et al. 2021; the recyclability of the adsorbent can be improved which
Siddiqui et al. 2019). further eliminates the high cost and challenging options such
Advancement in nanotechnology has motivated research- as filtration or centrifugation (Gao et al. 2020; Meteku et al.
ers across globe to design different nanomaterials owing to 2020; Rego et al. 2021; Sharma et al. 2022) (Fig. 1).
the multifaceted properties and thus applications of these
novel materials. Various porous organic and inorganic mate-
rials have been individually investigated for different envi- Properties of magnetic MOFs
ronmental applications. Another class involves organic–inor-
ganic hybrid porous materials typically synthesised by the The physical properties of MOFs are influenced by their com-
integration of the coordination chemistry toolkit and crystal positions and architectures. Design and analysis of MOFs with
engineering approaches, the realistic creation of molecule- complicated structural features are therefore essential for appli-
based framework with extraordinary properties known as cations with higher performance in a number of industries.
metal–organic frameworks (MOFs). Due to their adaptable Transition metal ions or clusters are combined with ditopic
hole topologies, diverse structures, customizable frames or polytopic organic ligands to form MOFs. The core–shell
with controllable properties and large surface area, MOFs design with functionalized magnetic nanoparticles, the self-
have become cutting-edge materials with applications in template technique with the metal ion generating the mag-
societal and industrially relevant sectors over the past three netic core-component, and implanting magnetic nanoparticles
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Fig. 1 Graphical representation

of scholarly publications in the
field of water purification. The
number of publications is calcu-
lated based on the science direct
data-base using keywords: Metal
organic frame-works based
nanomaterials for water purifica-
tion (metal organic framework
for water purification—Search |
ScienceDirect.com)
directly into the MOF composite matrix are some of the dif- be considered; these pathways will be covered in more detail
ferent methods utilised to add magnetism into MOFs. By in the following sections.
advancing from various oligomers to chains, layers, and 3D Adsorption has emerged as the most effective and important
networks, MOFs with magnetic nanoparticles have diverse method to remove the pollutants from water without second-
structures that offer various structure–property relationships. ary potential pollution with acceptable cost. As a fast, effi-
Adjusting metal and ligands is one method for controlling the cient, and economical physicochemical method, adsorption
structural properties of MOFs and the functional materials technology has been extensively used in wastewater treatment
created from them (Mukoyoshi et al. 2022). Most of the mag- for years, an example is depicted in Fig. 2c. The adsorptive
netic nanocomposites obtained to date are characterized by a efficiency strongly depends on the type of adsorbate, adsor-
core–shell structure in which magnetic nanoparticles act as a bent, and operating conditions. Moreover, the composite’s
core, and the shell is formed from an organometallic frame optical property determines how it interacts with light which
compound. The core–shell structure is characteristic of the is also influenced by its morphology, size, and shape. MOFs
Fe3O4@HKUST–1 magnetic nanocomposite, which includes with magnetic nanoparticles exhibit notable photocatalytic
a core of F e3O4 nanospheres functionalized with sulfonyl ace- properties that can be easily tuned and particularly used in the
tic acid and an HKUST–1 shell. Another strategy reported photodegradation of dye contaminants in the water. Moreover,
involves magnetic F e3O4@UiO-66 MOF supported on MOF these magnetic MOFs have the propensity to convert organic
and modified by a surfactant to enhance overall adsorption contaminants into harmless compounds when combined with
capacity as shown in Fig. 2a and b. Furthermore, depending on UV light. MMOF composites used in catalysis are occasion-
their composition, these MOF-based magnetic nanomaterials ally carbonised before to use in order to increase stability and
can be categorized as simple and complex magnetic nano- guarantee smooth recyclability. Thus, to put it in a nutshell,
composites. Simple magnetic nanocomposites consist of only owing to the versatility of MOFs, numerous reviews have been
magnetic nanoparticles and MOFs and the complex magnetic published concentrating on a variety of subjects connected to
nanocomposites include magnetic nanoparticles, MOFs, and their modifications, preparation, and applications. The fore-
a third component introduced into the composite to enhance going discussion surveys the research on the field of MOF-
its properties (Mukoyoshi et al. 2022). Furthermore, one of the based magnetic nanomaterials in particular for their focused
crucial physical characteristics of magnetic nanocomposites, applications in water treatment focussing on removal of heavy
particularly for their usage as adsorbent materials, is the high metals, harmful dyes, organic contaminants, and heavy metals
surface areas and porosity of the substance. From the stand- via photocatalytic and adsorption processes.
point of chemical design, the coexistence of magnetism and
porosity presents a challenge because these two properties are
incompatible. For example, while magnetic exchange interac- Preparation of MOF‑based magnetic
tions call for close proximity between the metal centres, which nanomaterials
are typically the spin carriers, porosity is typically favoured by
the use of long linkers, which are frequently too long for mag- There are conventional and non-conventional synthetic
netic ordering to exist. As a result, many synthetic pathways routes for the synthesis of magnetic MOFs. Different meth-
leading to the development of porous magnetic materials can ods of synthesis are, mechanochemical, electrochemical,
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Fig. 2 A Preparation of F e3O4@UiO-66@UiO-67/CTAB (Li et al. 2020a). b FESEM micrographs of La-MOF-NH2 and La-MOF-NH2@Fe3O4
(Valadi et al. 2020). c The interaction mechanism of Pb(II) and OTC onto Fe3O4@ZIF-8 (Wang et al. 2022)
sonochemical, flow chemistry, solvothermal, dry-gel, Solvo(hydro)‑thermal and iono‑thermal method

microwave, and spray-drying. In all routes, the basic reac-
tants are metal ion, ligands, and solvents. The schematic Solvothermal (or hydrothermal) and iono-thermal methods
representation of synthesis methods for MOF nanoparti- stand as fundamental approaches for crafting metal–organic
cles is represented in Fig. 3. frameworks (MOFs) and MOF-based magnetic nanomateri-
als with tailored properties. These techniques are pivotal in
the realms of materials science, chemistry, and engineering,
Fig. 3 Schematic representation

of different synthesis process of
MOF-based magnetic nanoma-
terials
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offering precise control over MOF crystal size, shape, and nanomaterials. In this method, the MOF precursor and mag-
composition (Lee et al. 2013). netic nanoparticles are dispersed in separate solvents and
In solvothermal (or hydrothermal) synthesis, metal ions then mixed together. The two solvents have different densi-
and organic ligands dissolve in a suitable solvent and are ties, resulting in the formation of a diffusion layer between
subjected to elevated pressure and heat within a sealed ves- them. As the MOF precursor diffuses from the high-density
sel, resulting in MOF formation. The inclusion of a solvent solvent to the low-density solvent, it begins to nucleate
accelerates MOF structure growth, yielding larger crystals and form MOF crystals around the magnetic nanoparti-
with specific properties. Careful modulation of temperature cles (Smaldone et al. 2010). The advantage of the diffusion
and pressure conditions permits the attainment of desired method is that it allows for more control over the size and
crystal characteristics. For example, researchers have used shape of the MOF-based magnetic nanomaterials compared
solvothermal methods to optimize MOF-5 nanoparticle to the slow evaporation method. Additionally, this method
size by adjusting synthesis parameters, leading to magnetic also enables the synthesis of MOF-based magnetic nanoma-
MOF-5 nanoparticles with enhanced organic dye adsorption terials with different morphologies and structures.
capabilities. Both the slow evaporation and diffusion methods have
Conversely, the iono-thermal method employs ionic their advantages and limitations for the synthesis of MOF-
liquids, which act as both solvent and MOF structure tem- based magnetic nanomaterials. For example, the slow evapo-
plate, in combination with metal ions. Ionic liquids, being ration method is a simple and easy-to-use method, but it
liquid salts at room temperature, facilitate precise control requires longer synthesis times and may result in the forma-
over MOF crystal size and shape. Recent work demon- tion of aggregates or large particles. Conversely, the diffu-
strated iono-thermal synthesis for crafting Fe3O4@ZIF-8 sion method allows for more control over the size and shape
core–shell magnetic nanoparticles with adjustable morphol- of the resulting nanomaterials, but it requires more special-
ogy and size, achieved through meticulous control of reac- ized equipment and may result in lower yields due to the
tion conditions (Zheng et al. 2014). formation of undesired products (He et al. 2021a).
Moreover, these techniques extend to tailoring MOF
properties. Solvothermal approaches yield Co-based and Microwave‑assisted method
Fe-based MOFs with distinct properties, including antifer-
romagnetism and catalytic activity. Modifications in syn- Microwave-assisted synthesis is a type of chemical syn-
thesis methods, such as those observed in Fe-MIL-88B thesis that utilizes microwave irradiation to heat the reac-
MOFs, underscore the versatility of solvothermal techniques tion mixture. This method has gained popularity in recent
(Rashed et al. 2022). years due to its ability to provide rapid and efficient heat-
ing, as well as its ability to selectively heat certain materi-
Slow evaporation and diffusion methods als, resulting in increased reaction rates and product yields.
The use of microwave-assisted synthesis for MOF-based
The slow evaporation method is a simple and widely used magnetic nanomaterials has been explored in several stud-
method for synthesizing MOF-based magnetic nanomateri- ies (Phan et al. 2023). For example, Masel and co-workers
als. In this method, the MOF precursor and magnetic nano- (Ni & Masel 2006) synthesized IRMOF-1, -2, and -3 using
particles are dissolved in a solvent, and the solvent is then microwaves-assisted method. The authors found that the
allowed to evaporate slowly at room temperature or under use of microwave irradiation significantly reduced the reac-
controlled conditions. As the solvent evaporates, the MOF tion time, resulting in the synthesis of IRMOF-1, -2, and
crystals begin to form around the magnetic nanoparticles, -3 within minutes, compared to several hours required by
resulting in the formation of MOF-based magnetic nano- conventional heating methods.
materials. The advantage of the slow evaporation method is Another study by Fuhua wei and co-workers (Wei et al.
that it is simple and does not require any specialized equip- 2022) reported the synthesis of magnetic MOF nanoparti-
ment, making it ideal for large-scale synthesis. Moreover, cles using a microwave-assisted method. The authors used
this method allows for control over the size, shape, and mag- microwave irradiation to heat the reaction mixture consist-
netic properties of the resulting nanomaterials by adjusting ing of terephthalic acid and hydrated samarium acetate. The
the synthesis conditions such as the concentration of the resulting MOF materials exhibits a good effect on removing
MOF precursor and the rate of solvent evaporation. Huo the organic dye Congo red (CR).
et al. (2012) synthesized a MIL-101 MOFs via magnetic The use of microwave-assisted methods for MOF-based
solid-phase extraction of polycyclic aromatic hydrocarbons magnetic nanomaterials has also been explored in combina-
in environmental water samples. tion with other techniques such as solvothermal synthesis and
On the other hand, the diffusion method is another com- electrospinning. For example, Zhang et al. (Aghayi-Anaraki
monly used method for synthesizing MOF-based magnetic &Safarifard 2020) reported the synthesis of F e3O4@ZIF-8
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magnetic nanocomposites using a combination of solvother- a magnet, making them suitable for adsorbent for efficient
mal and microwave-assisted synthesis methods. The authors Cu2+ removal application.
found that the use of microwave irradiation significantly The use of sonochemical methods for MOF-based mag-
reduced the reaction time and improved the homogeneity of netic nanomaterials has also been explored in combination
the resulting magnetic nanocomposites. The Fe3O4@ZIF-8 with other techniques such as solvothermal synthesis and
magnetic nanocomposites exhibited high saturation magneti- electrospinning. For example, Chen et al. (2018) reported
zation and excellent stability, making them promising candi- the synthesis of Fe3O4@ZIF-8 magnetic nanocomposites
dates for drug delivery and magnetic separation applications. using a combination of sonochemical and solvothermal syn-
In addition to the rapid and efficient synthesis of MOF- thesis methods. The authors found that the use of ultrasonic
based magnetic nanomaterials, microwave-assisted meth- waves significantly reduced the reaction time and improved
ods have also been shown to provide precise control over the homogeneity of the resulting magnetic nanocomposites.
the size, shape, and magnetic properties of the nanoparti- The Fe3O4@ZIF-8 magnetic nanocomposites exhibited high
cles. For example, Sijia Li and co-workers (Li et al. 2019) saturation magnetization and excellent stability, making
reported the synthesis of Fe3O4@MIL-100(Fe) magnetic them promising candidates for drug delivery applications.
nanocomposites using a microwave-assisted method. The In addition to the rapid and efficient synthesis of MOF-
authors synthesized F e3O4@MIL-100(Fe) via rapid micro- based magnetic nanomaterials, sonochemical methods have
wave heating in 30 min. The authors found that F e 3O 4@ also been shown to provide precise control over the size, shape,
MIL-100(Fe) magnetic nanocomposites as high-efficiency and magnetic properties of the nanoparticles. For example, He
adsorbent and catalyst for environmental remediation. e3O4@MIL-100(Fe)
et al. (2021b). reported the synthesis of F
magnetic nanocomposites using a sonochemical method. The
Sonochemical method authors found that by varying the ultrasonic power and reac-
tion time, they could control the size and morphology of the
Ultrasound is one the best energy source for the chemical resulting magnetic nanocomposites. The Fe3O4@MIL-100(Fe)
reactions. Ultrasound technique one of the simple techniques magnetic nanocomposites exhibited high saturation magnetiza-
which can reduce the reaction time and energy efficient. The tion and excellent stability, making them promising candidates
ultrasound technique works on the basis of the effect of acous- for magnetic separation and catalytic applications.
tic cavitation. The acoustic cavitation can be described as the
formation of hot spots which are generated by the growth and Microemulsion method
collapse of bubbles in the reaction solution. Sonochemical
synthesis is a powerful technique that uses ultrasonic waves The microemulsion method is a popular technique for the
to initiate chemical reactions. The use of this technique for synthesis of MOF-based magnetic nanomaterials due to its
the synthesis of MOF-based magnetic nanomaterials has been ability to produce nanoparticles with controlled size and
reported in several studies. Sonochemical synthesis offers shape. This method involves the use of a surfactant to form
several advantages, including rapid and efficient heating, a stable emulsion between two immiscible liquids, such as
precise control over reaction parameters, and the ability to oil and water. The reactants are then added to the emulsion,
produce nanoparticles with controlled size and morphology. and the nanoparticles are synthesized within the confined
The use of sonochemical methods for MOF-based magnetic environment of the microemulsion droplets. The resulting
nanomaterials has been reported in several studies. For exam- nanoparticles exhibit excellent stability and uniformity, mak-
ple, Lee et al. (2022) reported the synthesis of MIL-53(Fe) ing them suitable for a wide range of applications.
magnetic nanocomposites using a sonochemical method. The Several studies have reported the use of the microemul-
authors found that the use of ultrasonic waves significantly sion method for the synthesis of MOF-based magnetic
reduced the reaction time, resulting in the synthesis of MIL- nanomaterials. For example, Wang et al. (2016) reported the
53(Fe) faster than conventional method and the size of the synthesis of Fe3O4@MIL-101(Cr) magnetic nanocompos-
MIL-53(Fe) particles was reduced. The resulting magnetic ites using a microemulsion method. The authors found that
nanocomposites exhibited high absorption properties and has the use of a surfactant and a co-surfactant allowed them to
a potential application for an efficient, economic, and eco- form a stable microemulsion, which enabled the synthesis of
friendly wastewater purification process. Fe3O4@MIL-101(Cr) with controlled size and morphology.
Another study by Bui et al. (2022). reported the synthe- The resulting magnetic nanocomposites exhibited high satu-
sis of magnetic MOF nanoparticles using a sonochemical ration magnetization and excellent stability, making them
method. The authors used ultrasonic waves to initiate the promising candidates for absorption applications.
reaction between iron (III) ions and polystyrene sulfonate. Another study by Saikia et al. (2015). reported the syn-
The resulting magnetic MOF nanoparticles exhibited high thesis of magnetic MOF nanoparticles using a microemul-
saturation magnetization and could be easily separated using sion method. The authors used a surfactant to form a stable
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microemulsion between oil and water, which allowed them the use of templates or sacrificial materials to control the
to synthesize magnetic MOF nanoparticles with controlled size, morphology, and magnetic properties of the nanopar-
size and morphology. The resulting magnetic nanoparticles ticles. Template strategies can be broadly classified into
exhibited high saturation magnetization and excellent stability, two categories: hard-templating and soft-templating (Zou
making them suitable for catalytic applications. et al. 2022). In hard-templating, the MOF-based magnetic
The microemulsion method has also been used in combina- nanoparticles are synthesized using a template or scaffold
tion with other techniques such as solvothermal synthesis and material, such as mesoporous silica, zeolites, or alumina.
hydrothermal synthesis. For example, Folens et al. (2016). The template material is then removed through calcina-
reported the synthesis of F e3O4@MIL-101(Cr) magnetic tion or etching to obtain the final MOF-based magnetic
nanocomposites using a combination solvothermal synthesis nanoparticles (Doustkhah et al. 2021). In soft-templating,
method. The authors found that the use of a stable micro- the MOF-based magnetic nanoparticles are synthesized
emulsion allowed them to synthesize F e3O4@MIL-101(Cr) using a surfactant or other organic molecule as a template,
with controlled size and morphology, while the solvothermal which is then removed through solvent extraction or ther-
method improved the crystallinity and stability of the result- mal treatment.
ing magnetic nanocomposites. The Fe3O4@MIL-101(Cr) Several studies have reported the use of template strat-
magnetic nanocomposites used as adsorbent for arsenite and egies for the synthesis of MOF-based magnetic nanopar-
arsenate species in groundwater and surface water. ticles with controlled size, morphology, and magnetic
properties. For example, Meng et al. (2021) reported the
synthesis of zeolitic imidazolate framework-8 (ZIF-8) and
Post‑synthetic modification ZIF-67 nano- and micro structures template method, where
track-etched polycarbonate (PCTE) membranes were used
Post-synthetic modification (PSM) is a popular technique as a template. The authors found that the size and mor-
used for the functionalization of MOF-based magnetic phology of the ZIF-8 and ZIF-67 could be controlled by
nanomaterials, which involves the introduction of addi- varying the size and morphology of the track-etched poly-
tional functional groups onto the surface of the nanopar- carbonate (PCTE) membranes template.
ticles after their synthesis. PSM can be used to modify the Another study by Huang et al. (2012) reported the
physical, chemical, and magnetic properties of the nano- synthesis of hierarchically mesostructured MIL-101
particles, as well as to introduce specific functional groups metal–organic frameworks (MOFs) using a soft-tem-
that can be used for targeted applications. For example, plating method, where cetyltrimethylammonium bro-
PSM can be used to introduce carboxylic acid groups onto mide was used as a template. The authors found that the
the surface of MOF-based magnetic nanoparticles, which size and morphology of the mesostructured MIL-101
can then be used for drug delivery applications. metal–organic frameworks (MOFs) could be controlled by
Several studies have reported the use of PSM for the varying the CTAB/Cr3+ molar ratio used. The surfactant
functionalization of MOF-based magnetic nanoparticles. CTAB was found to play an important role in the prepara-
For instance, Tregubov et al. (2018) reported the function- tion of mesostructured MIL-101 nanoparticles.
alization of MOF-based magnetic nanoparticles with a Overall, template strategies offer a versatile and effec-
PSM technique. The authors found that the functionalized tive approach for the synthesis of MOF-based magnetic
magnetic nanoparticles demonstrate their application both nanoparticles with controlled size, morphology, and mag-
as a multimodal (MRI contrasting, magnetometric and opti- netic properties. With further optimization and develop-
cal labeling) and multifunctional (in vivo bioimaging, bio- ment, template strategies have the potential to play a
targeting by coupled receptors, lateral flow assay) agents. significant role in the synthesis of MOF-based magnetic
Overall, PSM offers a powerful tool for the functionalization nanoparticles for various applications.
of MOF-based magnetic nanoparticles, enabling the introduc-
tion of specific functional groups onto the surface of the nano-
particles for targeted applications. With further development Application in waste water treatment
and optimization, PSM has the potential to play a significant
role in the synthesis and functionalization of MOF-based mag- Photocatalytic degradation of dyes and toxic
netic nanoparticles. chemicals in water
Template strategies Photocatalytic degradation is considered one of the prom-

ising methods to degrade dyes, organic contaminants,
Template strategies are commonly used in the synthesis pharmaceutical drugs etc. from aquatic environment.
of MOF-based magnetic nanomaterials, which involves Thus, developing an effective photo-catalyst is very much
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necessary. Recently, metal organic frameworks (MOFs) the magnetic nanoparticle induced MOFs and the same
have brought significant attention attributable to their has been illustrated in Fig. 4, taking F e 3O 4-SiO 2/MIL-
outstanding performances, unique characteristics, and 101(Cr) composite (Azmoon et al. 2023). Upon light irra-
potential applications (Ning Liu 2020). However, the diation, the electrons are excited to the conduction band
usage of nanoscale MOFs in wastewater treatment still (CB) and holes are produced on the valence band (VB) of
shows some drawbacks, such as recycling inefficiencies photocatalysts. In the conventional mechanism, photoex-
and hindrance of total photocatalytic efficiency brought cited electrons of MIL-101(Cr) MOF moved to the CB of
by the recombination of photo induced charge carriers. Fe3O4-SiO2, and the holes of F e3O4-SiO2 transfer to the
Hence, fabricating MOF-based heterojunction is a feasible VB of MOF. According to this mechanism, the electrons
strategy to overcome such shortcomings. Creating mag- on the CB of F e3O4-SiO2 could not reduce O 2 molecules
netic composites based upon metal organic frameworks to the superoxide radicals (O2˙‾), since the ECB of Fe3O4
seems to be an appropriate route for the development of nanoparticle (0.83 eV) is less compared to the redox
these compounds. MOFs integrated with conventional potential of O 2/O 2˙ ‾ (− 0.046 eV vs. NHE). But, in the
semiconductors possess a higher specific surface area Z-scheme mechanism, the photo-generated electrons in
thus leading to the formation of higher number of active CB of F e3O4-SiO2 moved to the VB of MOF and recom-
sites which in turn has greater possibility of interaction bined with the holes. As a result, the O2 molecules can be
between active sites and different reactants, thus ensuring easily reduced by electrons in the CB of MOF to gener-
greater feed conversions. Additionally, the MOFs higher ate the O 2˙‾ since the VB potential is greater compared
specific surface area may bring about less aggregation of to the redox potential of the O 2/O 2˙‾ couple. Hydroxyl
numerous magnetic nanoparticles namely Fe3O4, Fe2O3, anions ( HŌ ) are not oxidized into hydroxyl radicals
MgFe2O4, MnFe2O4, CoFe2O4, or N iFe2O4 henceforth bet- (HO˙) because of the lower VB potential of MIL-101(Cr)
ter dispersion of these nanoparticles on MOFs surface (2.08 eV) and F e 3O 4 (2.13 eV) compared to the redox
(Bagherzadeh et al. 2020). Besides, magnetic nanoparticle potential for oxidation (2.72 eV/NHE). More importantly,
induced MOFs have been designed to delay the recombi- the incorporation of F e3O4 magnetic nanoparticles to the
nation of photo-induced charge carriers and to enhance MIL-101(Cr) MOF reduced the band gap of nanocompos-
the photo-catalytic performance of multi-pollutants. The ite therefore can be active under light illumination. Based
photo-induced electrons usually transfer from the light- on the Z-scheme mechanism, the movement of electrons
harvesting MOFs to magnetic nanoparticles thus reducing between the binary structure can favour the electron–hole
the recombination of charge carriers. These unique photo- pair separation, minimizes the recombination rate which
catalysts helps to achieve effective recyclability. However, in turn increases the lifetime of the photo-generated elec-
two possible charge transfer mechanisms are possible with trons and holes (Azmoon et al. 2023).
Fig. 4 Possible charge transfer mechanisms in the magnetic nanoparticle induced MOFs (Re-produced from Parisa Azmoon et al. (2023) with
permission)
13
Some of the works related to photocatalytic degradation that the synthesized nanocomposite with 30 wt% of UiO-
of organic molecules using MOF induced magnetic nano- 66 MOF showed greater photo-catalytic efficiency under
particles have been listed in Table 1. For example, Xiaohan the visible-light irradiation towards the photo-degradation
Zhang et al. (2022a) synthesized magnetically recoverable of methyl orange (MO), rhodamine B (RhB) as well as the
Z-scheme photocatalyst, MOF (Mil-88B)/ZnFe2O4/Fe2O3 binary dye solution which consists of a mixture of RhB and
perforated nanotube for photo-degradation of ciprofloxacin. MO compared to pure BiFeO3, bare MOF, and other sam-
The perforated nanotube as well as the Z-scheme transfer ples. Vo et al. (2021) proposed the synthesis of M gFe2O4@
pathway manifested greater light absorption including inter- UiO-66 (Zr) (MFeO@UiO) nanocomposites via in-situ
facial and bulk-phase segregation of photo-generated charge, assemblies with differing compositions for tetracycline (TC)
which in turn led to better photocatalytic performance for removal. Deposition of UiO-66(Zr) MOF onto MgFe2O4
the removal of ciprofloxacin. Likewise, Afsaneh Faraji et al. nanoparticles resulted in a composite structure possessing
(2021) used wet chemical method for the successful syn- a lower bandgap energy between 2.28 and 2.60 eV com-
thesis of ZiF-8/NiFe2O4 photo-catalyst for the photo-deg- pared to parent UiO-66(Zr) framework (~ 3.8 eV). Further-
radation of methylene blue (MB) dye. The ZiF-8/NiFe2O4 more, the MFeO@UiO nanocomposite manifested improved
photo-catalyst exhibited very compelling photocatalytic porosity and better magnetic separation property. The syn-
performance for MB removal under visible-light irradia- thesized nanocomposite showed TC removal efficacy of 94%
tion with a degradation ability of 94% in 120 min with 30 within 120 min of visible-light illumination and the effective
wt% of N iFe2O4. Similarly, Samin Bargozideh et al. (2020) photo-degradation efficiency could be accredited to higher
attempted to design a p-n heterojunction photo-catalyst via interfacial charge transfer at the heterojunction as well as the
solvothermal method by synthesizing magnetic UiO-66/ synergistic effect between the semiconductors. The Ky Vo
BiFeO3 nanocomposite for the photo-degradation of methyl team (Vo et al. 2022) proposed microwave-assisted synthesis
orange (MO) and rhodamine B (RhB). The results suggest of MgFe2O4@UiO-66(Zr)-NH2 nanocatalyst for collective
Table 1 Comparison table of different MOF-supported magnetic nanoparticle catalysts used for photocatalytic degradation of molecules
Catalyst Organic molecules Degradation efficiency Time (min) Target Catalyst (mg/L) Reference
(%) molecule
(mg/L)
Fe3O4@MIL-53(Fe) Ibuprofen 99 60 10 400 (Ning Liu 2020)

Fe3O4@MIL-88B(Fe) Rhodamine B 99.8 80 100 20 (Zhaokui Jin 2016)
Fe3O4@MIL-100(Fe)- Methylene blue 99 120 50 100 (Zhang et al. 2013)
H2O2
Fe3O4-SiO2@MIL- Oilfield produced 95.17 (visible light) 150 600 500 (Azmoon et al. 2023)
101(Cr) water 96.6 (UV-light)
Fe3O4@ZIF-67 Congo red 94 30 20 10 (Weihua Guan 2017)
Fe3O4@ZIF-8/SPC Methylene blue 98.9 30 10 1000 (Saeed Sajjadi 2018)
Fe3O4@MOFUIO-66@ Malachite green and 99 (MG) 40 100 20 (Mingxin Zheng 2020)
TzDa-COF congo red 97 (CR) 120
MgFe2O4@UiO-66(Zr) Tetracycline 94 120 200 40 (Vo &Kim 2021)
MgFe2O4@UiO- Tetracycline 92 160 220 70 (Vo et al. 2022)
66(Zr)-NH2
CoFe2O4@MIL-53 Direct red 23 99.35 80 80 20 (Bagherzadeh et al.
(Fe) 2020)
NiFe2O4@ZIF-8 Methylene blue 94 120 10 50 (Faraji et al. 2021)
Fe3O4@MIL-53(Fe)/ Ibuprofen 100 180 10 250 (Liu et al. 2022)
BN
γ‑Fe2O3@ Amoxicillin 88 60 10 400 (Al-Musawi et al. 2023)
SiO2@ZIF8-Ag
Ag3PO4@MIL-101/ Rhodamine B 93 30 10 20 (Tianhong Zhou et al.
NiFe2O4 2018)
BiFeO3@UiO-66 Rhodamine B and 88.7 (RhB) 180 10 10 mg (Samin Bargozideh
Methyl Orange 89.3 (MO) 2020)
MOF(NiFe)-derived Tetracycline > 85 15 15 20 (Rashid et al. 2023)
NiSe- Fe3O4/C
13
photocatalytic degradation and adsorption of tetracycline. Interestingly for wastewater treatment, the recombina-
The designed photocatalyst nanohybrids demonstrates tion rate can be reduced by introducing hydrogen peroxide
higher magnetic properties and surface area. (H2O2) as an electron acceptor, same like S iO2. In addition,
Similarly, Fe3O4@MOFs exhibits high stability, disper- the generated hydroxyl (˙OH) radical, as an effective oxi-
sion, and greater catalytic efficiency. Weihua Guan et al. dant possess a high standard potential. Thus, by introducing
(2017) designed a photocatalyst F e3O4@ZIF-67 with flower- H2O2 to the core–shell Fe3O4@MOFs heterostructure, the
like heterostructure for the photo-degradation of congo red light induced electrons of MOF particles can interact with
(CR) under visible light irradiation. The proposed method H2O2. Thus, the utilization efficacy of the photo-induced
shows the uniform and consistent distribution of F e3O4 par- electrons can be increased (Hongying Zhao et al. 2015). For
ticles on the surface of ZIF-67 MOF microspheres, bestow- example, Zhang et al. (2013) designed a core–shell based
ing the photocatalyst with greater recyclability and magnetic photocatalyst, Fe3O4@MIL-100 for the photo-degradation
separation. Likewise, Zhaokui Jin et al. (2016) developed a of MB dye. The synthesized Fe3O4@MIL-100 (Fe) exhib-
photocatalyst, Fe3O4/MIL-88B (Fe) for the photo-degrada- ited a photo-degradation ability for MB removal under both
tion of rhodamine B and methylene blue. The hierarchical visible light and UV–vis irradiation. Nevertheless, the MB
nano-architectures developed via metallic node reduction photo-degradation efficiency was very low around 35%,
facilitate inventive strategy to bestow the nanocomposites therefore H2O2 was incorporated into the dye solution in
magnetic functionality including the light harvesting abil- order to enhance the degradation efficiency. Interestingly,
ity at visible regions; perhaps, this may be because of the upon addition of H2O2, greater photo-catalytic efficiency of
spectral overlap between Fe3O4 nanoparticles and Fe3-µ3-oxo 99% was achieved for MB removal this is mainly because the
cluster including the development of huge micro/meso H2O2 acts as an electron acceptor which could diminish the
porous channels, efficient transport, and wider absorption. electron–hole pair recombination, in turn strengthening the
Also, the literature suggests that creating a perfect photo-degradation efficiency. However, in the MOF matrix,
core–shell hetero structures is a great idea for the photo- the photo-generated holes are shell-localized, and the trans-
degradation of molecules with F e3O4 nanoparticles as the ference of holes to F e3O4 core depends mainly on shell
core and MOF matrix as the shell, since the shell can con- thickness. Thus, Hongying Zhao et al. (2015) came up with
ceal the F e3O4 particles from the exciting radiation. Never- an idea to regulate the shell thickness along the presence of
theless, core–shell hetero-structures, for example, F e 3O 4@ H2O2. Their team also studied the effect of shell thickness
MOFs represent type l core–shell band alignment (Hongy- on photo-generated electron reactivity towards dye degrada-
ing Zhao et al. 2015). The electrons from the conduction tion. The results exhibit that by introducing H2O2 and Fe3O4
band of the core Fe 3O 4 nanoparticles are less cathodic core together, the separation of photo-induced electrons and
compared to that of MOFs shell, likewise the holes from holes of MOF nanostructures could be promoted, which in
the valence band (VB) of the Fe3O4 core assist charge-car- turn can boost the photo-degradation performance of MOF-
rier recombination. As a consequence, the photocatalytic based catalysts. Also, the photocatalytic efficacy of Fe3O4@
activity of core–shell Fe3O4@MOFs could be suppressed MIL-100 (Fe) could be ameliorated by regulating the thick-
greatly when compared to pure MOFs (Hongying Zhao ness of MIL-100 (Fe) MOF shell by differing the assembly
et al. 2015). However, this charge-carrier recombination cycles. With optimal thickness of ≈ 50 nm, more number of
can be prevented by coating F e3O4 nanoparticles with an photo-induced holes are localized in MOF shell which can
intermediate layer like SiO2. For example, Azmoon et al. easily access the core F e3O4 magnetic nanoparticles, this in
(2023) synthesized visible-light driven composite of MIL- turn helps more electrons to productively react with H2O2 to
101(Cr)/Fe3O4-SiO2 for photocatalytic degradation and give rise to ˙OH radicals. This approach further enhances the
adsorption of oilfield produced water. The narrow bandgap photo-catalytic ability of MOF heterostructure based pho-
energy and high-specific surface area, as well as the charge tocatalyst consisting of MOFs and magnetic nanoparticles.
carrier separation via the Z-scheme heterostructure, led to Furthermore, calcination treatment was proposed to addi-
the advancement of binary composite photocatalyst proper- tionally enhance the photo-catalytic and magnetic proper-
ties. The formation of silica-coated Fe3O4 with MIL-101 ties of nanoparticle decorated MOFs. For example, Liu et al.
(Cr) enhanced the photocatalytic activity because of the (2020) prepared magnetic Fe3O4@MIL-53 (Fe) photocata-
reduction in band gap to outreach the visible light region. lyst from calcination for the photo- degradation of ibupro-
Also, the photo-generated electron–hole pair recombina- fen. The results suggest that the MIL-53 (Fe) and Fe3O4
tion rate was minimised by enhancing the charge separation co-existed after calcination (at 400 ˚C) of MIL-53 (Fe) and
because of the migration of electrons and holes within the pearl-like Fe3O4 effectively combined with MIL-53 (Fe).
two catalysts. Al-Musawi et al. (2023) prepared γ-Fe2O3@ Fe3O4@MIL-53 (Fe) nano-composites demonstrated greater
SiO2@ZIF8-Ag nanocatalyst for the photo-degradation of photocatalytic performance because of their unique struc-
amoxicillin in aqueous solution. ture as well as the electron transfer between MIL-53 (Fe)
13
and Fe3O4 by attaining nearly 99% of ibuprofen degradation example, Mingxin Zheng et al. (2020) successfully synthe-
efficiency in presence of H 2O2. The effectual photocatalytic sised Fe3O4@MOFUIO-66 heterostructure and encapsulated
activity could develop from the increased separation of in a Triazine-based COF matrix for the photo-degradation
photo-excited electron–hole pair. Similarly, Saeed Sajjadi of anionic dyes by specifically following a certain synthesis
et al. (2018) incorporated zeolitic imidazolate framework order. The developed new matryoshka Fe3O4@MOFUIO-66@
(ZIF-8) lattice to activate sodium percarbonate (SPC) for TzDa-COF nanocatalyst manifests accelerated photo-degra-
the photo-degradation of MB dye. SPC acts as H 2O2 carrier dation efficiencies of anionic dyes such as malachite green
to generate.OH radicals for the photo-degradation of dye. (MG) and CR dyes regardless of their concentrations. More
Also, increase in Fe3O4@ZIF-8 dosage and SPC concentra- interestingly, the degradation efficiency of the COF-sup-
tion enhanced MB catalytic degradation. This is because ported nanocatalyst (Fe3O4@MOFUIO-66@TzDa-COF) was
the increase in SPC concentration promotes the release of greatly determined by the order of the incorporated nanopar-
substantial amounts of H 2O2 in bulk solution, which in turn ticles for example, the inner core being the F e3O4 nanopar-
generates more.OH radicals for better decomposition of tar- ticles, the medium bridge is UIO-66 MOF, and finally, the
get molecules. outer shell consists of TzDa-COF matrix. The chemical dis-
To further enhance the photo-catalytic activity of various tinctness of linkers and nodes in COFs and MOFs including
molecules, conventional Fe3O4 magnetic nanoparticle was the metal clusters or inner metal ions bring forth an effectual
replaced with various binary metal oxides in Fe3O4@MOFs platform for the development of multifunctional nanocata-
heterostructures. For example, Bagherzadeh et al. (2020) lyst for various dye degradation. Similarly, Navarathna et al.
prepared MIL-53 (Fe)/CoFe2O4 magnetic nanocomposite for (2019) designed MIL-53-FeMOF/magnetic magnetite/bio-
the photo-degradation of direct red 23 (DR23) dye under char nanocomposites for both photocatalytic degradation and
LED light irradiation. An effectual photo-induced charge adsorption of Rh B dye. Mil-53-Fe MOF was developed on
transfer as well as separation was greatly achieved with this already prepared Douglas fir type biochar/ F e3O4 adsorbent
nanocomposite. The same group (Bagherzadeh et al. 2021) hybrid. The Douglas fir biochar phase assist to effectively
also developed GO based magnetic nanocomposite, MIL- disperse the MOF nanoparticles to impart additional stabil-
101(Fe)/CoFe2O4/(3%)GO for the photo-degradation of ity to the MOF, serves as secondary adsorption site for oxy
DR23, and reactive red 198 (RR198) dyes as well as tetra- anion, organic contaminant and heavy metal and to mitigate
cycline hydrochloride (TC-H) antibiotic. In MIL-101(Fe)/ particle aggregation. Finally, Liu et al. (2022) designed a
CoFe2O4/(3%)GO nanocomposite, the GO’s presence as a ternary photocatalyst BN/Fe3O4/MIL-53(Fe) for degrada-
strong electron acceptor led to the greater segregation of tion of Ibuprofen by visible light aided photocatalytic acti-
charge carriers which in turn led to the reduction of their vation of persulfate molecule. The designed photocatalyst
recombination. Also, the presence of GO helped to increase possessed narrower band gap and rougher surface which in
the visible-light absorption range and this nanocomposite turn assisted to attain greater photocatalytic performance
also demonstrated good permanence in terms of reusability with photo-degradation efficiency of 100% within 180 min.
and stability. Similarly, Nirumand et al. (2018) designed ter- Rashid et al. (2023) proposed to synthesize flower-like NiSe-
nary magnetic photo-catalyst, MIL-101(Cr)/RGO/ZnFe2O4 Fe3O4/CS-scheme heterostructure via solvothermal strategy
with 30 wt% of ZnFe2O4 magnetic nanoparticle for sono- from the Ni/Fe-MOF sacrificial template for the photo-deg-
degradation of various dyes (such as CR, MB, RhB, and radation of tetracycline antibiotic in an outlined microfluidic
MO) in aqueous solution. The obtained results display that photoreactor with spiral shape. The results exhibit that the
the ternary MIL-101(Cr)/RGO/ZnFe2O4 nanocatalyst shows combining of NiSe-Fe2O4 and carbon sheath can stimulate
superior performance towards the sono-degradation dyes greater light-harvesting potentiality and photo-induced
compared to their binary nanocomposites. The augmented charge separation as well as transfer efficacy caused vigor-
photo-catalytic efficiency could be due to the quick forma- ous photocatalytic performance.
tion as well as separation of charge carriers in MIL-101(Cr)/ In conclusion, synthesizing magnetic composites based
rGO and ZnFe2O4 and their shift to the surface of GO sheets. upon metal organic frameworks seems to be an effective
Besides, the higher specific surface area of MIL-101(Cr)/ approach to develop highly efficient photocatalyst for the
rGO heterostructure and magnetic property of Z nFe2O4 nan- degradation of dyes and other organic molecules. These
oparticles jointly upgrade the phot-degradation efficiency of hybrid catalysts help to reduce/slow down the recombination
numerous dyes. of photo induced charge carriers and these photocatalyst can
Nevertheless, slight modification to MOF@magnetic be easily recovered and recycled using a magnet without any
nanoparticles have been proposed to further ameliorate the consequential loss in photocatalytic activity. The magnetic
photocatalytic behaviour of the nanohybrids by encapsu- nanoparticle@MOFs show high-photo-degradation effi-
lating covalent organic framework (COF) matrix to MOF ciency and the enhanced efficiency could be ascribed to the
core shells or by incorporating biochar to the matrix. For synergistic effect between the semiconductors and also due
13
to the effective interfacial charge transfer at the heterojunc- considered an interesting strategy. The section explores the
tion. However, the charge-carrier recombination can be fur- MOF-based magnetic nanomaterials that have been reported
ther prevented by creating an intermediate layer with SiO2, for the removal of organic pollutants from the water (Awad
H2O2, GO, and so on. The creation of these intermediate et al. 2020; Tchinsa et al. 2021).
layers increases the photocatalytic activity to a great extent The Fe3O4 magnetic nanoparticles are widely employed
because of the reduction of the band gap which in turn helps with the MOFs; Antonio and his group reported compos-
to outreach the visible light range. Also, the recombination ite based on MIL-101 and F e3O4 nanoparticles (Fe3O4/
rate of photo-generated electron–hole pairs was largely MIL-101) as adsorbent for the removal of anthracene, a
reduced by increasing the charge separation because of the polycyclic hydrocarbon which offers great environmental
migration of electrons and holes between the two catalysts. threats. The maximum adsorption capacity was 12.7 mg/g
at pH 6 in 1 h of exposure, accounting for more than 95%
Adsorption of organic pollutants of anthracene removal as depicted in Fig. 5 (Lu &Astruc
2020, Tirado-Guizar et al. 2020). Fe3O4@SiO2@UiO-67, a
Billions of tonnes of organic chemicals including pesticides, different innovative MOF-based smart adsorbent, was also
personal care products, organic colours, and pharmaceuticals used for the detection and elimination of harmful organo-
are produced every year, which has led to increase in organic phosphorus pesticide from water. With a high-adsorption
pollutants leading to one of the most significant environmen- capacity (256.54 mg g−1), good reusability, and a low detec-
tal issues, following heavy metals in water. Furthermore, tion limit (0.093 mg L −1) for glyphosate, the combination
due to their resistance and persistence in the environment, affects the fluorescence intensity of the smart adsorbent
the elimination of organic pollutants from water is a subject (Yang et al. 2018b). Lu et al. synthesized nano-cellulose/
of considerable interest across the globe and dense organic MOF-derived carbon-doped CuO/Fe3O4 composite catalyst
pollution poses a grave threat to the ecosystem’s stability was successfully fabricated for reduction of 4-nitrophenol
as well as the health of all species. In order to address this with good reusability/recyclability (Lu et al. 2019). Also,
issue, research on exploring various materials to develop the high-adsorption capacities of congo red (dye) and doxy-
cutting-edge technologies continues to grow exponentially cycline (antibiotic) were used for the adsorption of organic
every year. The use of a material based on metal–organic pollutants using bioinspired ZIF-8 with magnetic F e 2O 3.
framework (MOF) with large pores and high surface area This novel magnetic ZIF-8 micromotor also demonstrated
and magnetic nanoparticles which are easily recycled is outstanding stability and reusability in aqueous solution,
Fig. 5 A Adsorption mechanism

for the Magnetic MOF compos-
ite against anthracene. b VSM
hysteresis curve of the Fe3O4
and Fe3O4 /MIL-101 MOF
composite. c TEM micrographs
of the composite F e3O4/MIL-
101. d Time effect in adsorption
capacity of anthracene by Lang-
muir mechanism (Tirado-Guizar
et al. 2020)
13
indicating that their great potential for future use in water novel poly(4-vinyl pyridine)-functionalized magnetic Al-
treatment (Liu et al. 2019). Owing to the magnetic properties MOF nanocomposite. The nano conjugates exhibited rough
of metal Ni nanoparticles, Ni/C aerogels via self-assembly surface, a porous structure, a large surface area, several
of Ni-MOFs were prepared for advanced treatment of oily functional groups, and exceptional magnetic properties.
wastewater; specifically, nitrobenzene and furfural conver- The nanocomposite and the adsorption process described
sions were carried out. The water induced assembly mecha- followed the pseudo-second order and Freundlich kinetic
nism of Ni-MOF hydrogel was investigated by adjusting the models which promoted the rapid adsorption of naproxen
ratio of water/ethanol and molecular dynamics simulation, of 31.67 mg/g. From the adsorption–desorption studies, the
demonstrating that strong interaction existed between water adsorbent showed an outstanding adsorption performance,
and Ni-MOFs via the Coulomb force for the assembly of maintaining 60% of its initial adsorbing capacity up to 10
Ni-MOFs. The produced Ni/C aerogel exhibited nanofiber repeated cycle (Li et al. 2020b). Furthermore, removal of tet-
morphology and hierarchical porous structures with ultra- racycline, an antibiotic over magnetic NiCo/Fe3O4-MOF-74,
light, superhydrophobic properties, elasticity, and high-spe- exhibited notable adsorption with a high removal efficiency
cific surface areas, ensuring the highly accessible excellent that reached 94.1% within 5 min, which is much higher than
adsorption and catalytic capacity for oil/water separation. that of non-magnetic counterpart without Fe3O4, and upto
Especially, the highest adsorption efficiency for motor oil after 5 cycles, the MOF modified with F e3O4 maintained a
(38.99%) and carbon tetrachloride (48.77%) (Su et al. 2020). high-adsorption ability. The open metal sites that can form
Graphene oxide (GrO) and carbon nanotubes (CNTs) a stable metal–ligand with the antibiotic molecules are most
hybrid nanocomposites decorated with a series of new likely responsible for the majority of the interaction between
absorbents based on Cu-BDCMOFs are used to target Bis- the adsorbent and analyte (Xiao et al. 2020).
phenol A (BPA) in water remediation. The exceptional The well-established benefit of employing magnetic par-
adsorption capacities of the hybrid nanomaterials—182.2 ticles in composite materials is that they can be success-
and 164.1 mg/g towards the elimination of BPA—were fully separated using an external magnet without the need
significantly higher than the 60.2 mg/g for Cu-BDC MOF for further centrifugation or filtration procedures. Rapid
that the Freundlich model best predicted. An analysis of the magnetic solid-phase extraction of organic pollutants from
kinetics of the produced nanoparticles revealed that they ambient water samples is demonstrated by the MOFs. It is
could eliminate the maximal quantity of BPA from water in believed that the extraction of different organic pollutants
30 min. The exothermic and spontaneous BAP adsorption is aided by hydrophobic and π-π interactions between these
mechanism onto the hybrid nanocomposites. Throughout organic pollutants and the framework molecules, as well as π
the BPA adsorption process, the interactions between the -complexation with the Lewis acid sites in the pores of MIL-
hybrid nanomaterials and BPA were crucial (Ahsan et al. 101 (Lu &Astruc 2020). All of above literature point to the
2019). Furthermore, Cu-BTC MOF hybrid when modi- potential of MOF-based smart adsorbents for simultaneous
fied with Fe3O4 magnetic nanoparticles was tested for the organic pollutant adsorption/detection and removal, offering
adsorption of methylene blue as a model organic pollutant a workable solution for water quality monitoring and waste-
resulting in a high adsorption capacity (Jabbari et al. 2016a). water treatment. Long-term development of highly effective
Rasheed et al. have well reviewed magnetic MOF-nanocom- and ecologically suitable nanomaterials with high recycla-
posites for efficient removal of pharmaceuticals and per- bility for wastewater treatment at cost-effective levels will
sonal care products commonly known as PPCP. The review be a significant challenge, especially for environmentally
highlighted the use and toxicity of salicylic acid (SA), a friendly self-cleaning materials. A thorough assessment of
type of phenolic acid with extensive utilization in organic the dangers and potential effects of nanomaterials on human
synthesis, and acetylsalicylic acid (ASA), commonly used health and ecosystems, notably potential cellular toxicity,
non-steroidal anti-inflammatory medicine. Both pollutants must be evaluated. Thus, incorporating magnetic Nanoma-
are introduced into the ecosystem directly from wastewa- terials would substantially minimize this risk as they are
ter as well as indirectly as metabolites of other chemical easily recoverable.
products (Rasheed et al. 2020). To test the effectiveness of
magnetic Fe3O4@SiO2@ZrO2-UiO-66-NH2 nanocomposites Adsorption of dyes
as adsorbents for the removal of SA and ASA from aque-
ous solutions, Zhang et al. developed this magnetic MOF. Dyes being major organic contaminants possess several
Even after being used three times, the synthetic compos- functional groups, which would offer versatile interactions
ites’ adsorption capacity persisted at up to 77% and 70% for with MOFs. Depending on the surface charge of MOFs,
SA and ASA, respectively (Zhang et al. 2019b). Another electrostatic interactions between MOF and the charged
pharmaceutical contaminant, viz., naproxen was success- contaminant dyes are expected, with an important role of
fully adsorbed and removed from water samples using a solution pH. MOFs functionalized with –NH2, -OH, -SO3H,
13
and –COOH tend to adsorb the dye molecules with hydrogen of CR and Fig. 6 depicts the hypothetical mechanism of CR
bonding (Zhang et al. 2019a). There exist several reports degradation; CR’s attachment to Fe3O4@ZTB-1 is caused by
inferring π-π stacking or interactions between the dye mol- electrostatic interactions and hydrogen bonds.
ecules and the MOF molecules having π-bonding system Magnetic MOF nanocomposite, F e 3 O 4 @MIL-101,
(Ning et al. 2017; Zhang et al. 2019a). Pore selective and was synthesized by heterogeneous co-precipitation strat-
size selective adsorptions are also expected depending on egy, which efficiently removed an anionic dye fluorescein
the pore size of MOFs and the adsorbing contaminant mol- sodium (FS), xylenol orange (XO), and methyl orange (MO)
ecules. Relaying on several mechanisms of adsorption, ver- from aqueous phase. The F e3O4@MIL-101 showed a better
satile metal and organic moieties–based MOFs, nanocom- adsorption efficiency than the MIL-101 (Jiang &Li 2016).
posites of carbon, functionalized MOFs, and biodegradable Along with good surface area and pore volume, F e 3O 4@
MOFs are developed and are discussed in this section (Abd MIL-101 presented a zeta potential of 39.5 mv and offered
El-Monaem et al. 2023; Eltaweil et al. 2023; Omer et al. good electrostatic attraction towards anionic dyes. Mag-
2021). netic MIL-100(Fe) MOF is also experimented to remove
The magnetic MOF F e3O4@ZTB-1 was able to adsorb rhodamine B (RB) (Liu et al. 2016b). However, there was
congo red (CR) with in 20 min and the maximum adsorption an electrostatic repulsion towards cationic dyes and hence,
capacity was 458 mg/g (Han et al. 2019). There exists an no adsorption for cationic dyes. Nevertheless, the copper-
adsorption of ZTB-1 on Fe3O4 surface due to the electro- based magnetic MOF, Cu3(BTC)2 showed a greater adsorp-
static interaction between the negative charges on the sur- tion removal efficiency for methylene blue (MB), which is a
face of F e3O4 and Z n2+ ions of ZTB-1. Furthermore, with cationic dye, due to high surface porosity (Zhao et al. 2015).
Fe3O4@ZTB-1, the induced dipole produced by Fe3O4 can Zeolitic imidazoloate framework-67, ZIF-67, fabri-
cause the ZTB-1 molecule to develop a temporary dipole, cated into magnetic ZIF-67 demonstrated an adsorption
increasing the deformability of ZTB-1 and the orbital over- of 738 mg/g for MO attributing to the high porosity and
lap between the oxygen and zinc atoms, promoting electron also the Lewis base nature of coordinated CO2+ centrals of
transfer from oxygen to zinc. This has increased electron- MOF (Yang et al. 2018a). The cages of magnetic ZIF-67
withdrawing power of the oxygen atoms in carboxylate possessed a pore size of 10 Å, and despite of adsorption of
group C = O bonds and led to the degradation of CR. Addi- both MB and MO, the MOF was able to selectively separate
tionally, it made it easier to form hydrogen bonds with the MO from a mixture of MB and MO solution ascribing to the
hydrogen atom of -NH2 group in CR. F e3O4@ZTB-1 nano- charge on the dyes. Especially at pH 9.4, the –SO3− ions of
material was saturated in a high concentration of CR before MO presents a strong attraction towards the Co2+ centrals of
having its FT-IR spectra analysed and compared to deter- MOF, whereas, at acidic pH, the competition with hydrogen
mine how it adsorbs. It is proved by authors that the hydro- ions occurs, and thereby, adsorption reduces. Lijin Huang
gen bonding interactions between oxygen atoms in carboxy- and group synthesized magnetic MOF, by coating Zr-MOF
late groups from Fe3O4@ZTB-1 and hydrogen atoms in the on Fe3O4@SiO2 core, Fe3O4@SiO2@UiO-66 and even its
-NH2 groups from the CR molecule control the adsorption amino derivatives, which were able to selectively separate
Fig. 6 Mechanism of adsorption

of congo red dye on magnetic
Fe3O4@ZTB-1 MOF (adopted
from Han et al. (2019))
13
the anionic and cationic dyes, even up to 6 cycles (Huang magnetic MIL-101(Al) (Liu et al. 2016a). MOF-74(Zn/
et al. 2018). Some of the magnetic MOFs especially used for Fe)-derived magnetic porous carbon was employed to get
dye adsorption are described in Table 2. 370 mg/g of MB and 239 mg/g of MO (del Rio et al. 2022).
Besides, in addition to experimental outcomes, the results Along with magnetic MOFs, the carbon hybrids of
of selective separation of dyes using MOF were validated the same have also gained interest. Carbonization, nano-
by Density Functional Theory (DFT) findings as well by composites of graphene, graphene oxide (GO), reduced
Farshad Valdi and group (Valadi et al. 2020). Lanthanum- graphene oxide (rGO), and carbon nanotubes (CNT) have
based magnetic MOF (La-MOF-NH2@Fe3O) selectively been explored in combination with MOF precursors to
separated CR in 2 min (up to 92.02%) from a mixture of obtain carbon based magnetic MOFs. A novel core–shell
cationic and anionic dyes. The adsorption was spontane- ZIF67@C-MOF-74 structure using MOF-74(Co) and
ous and endothermic. Perhaps, the DFT calculations based 2-methylimidazole (Del Rio et al. 2020). This hybrid
on valance band and conduction band molecular orbitals, material obtained carbonization demonstrated a greater
chemical potential, and electrophilicity index showed the adsorption efficiency for CR and faster extraction uptake.
interaction of CR with MOF. pH of a dye solution played an A hybrid magnetic nanocomposite F e3O4/Cu-BTC@Gra-
important role in imparting the charges on dyes and MOF, phene was developed as shown in Fig. 7 (Jabbari et al.
which facilitated the strong guest–host interactions via 2016b). The graphene layer diminishes the aggregation
phisochemisorption of CR on considered amino function- and enhances the forces of dispersion within the MOFs.
alized MOF. The amine groups presented the active sites These will also add an advantage of formation of platform
and was confirmed by DFT calculations. The importance of with small pores and MOFs of varied size and morphol-
amine functionalities in improvising the adsorption capacity ogy. Compared to individual parent materials, prepared
of MOF is also proven by Quinzhi Wang and group (Wang hybrid exhibited higher adsorption of MB. ZIF-67 on
et al. 2021). Amine-functionalized magnetic Fe-, Ti-, and wood is carbonized to obtain the carbon based Co com-
Zr-based MOFs were experimented to remove azo dyes pre- posites (Ma et al. 2022). The hierarchical porous assem-
sent in soft drinks. The π-π stacking, hydrogen bonding, and bly of wood assist the swift passage of CR and MB dyes
surface active sites offers a cooperative effect and enhances leading to 117.03 and 805.08 mg/g of adsorption, respec-
the adsorption of azo dyes (Zhang et al. 2019a). Malachite tively. [Co3(BTC)2(H2O)12] was carbonized to give mag-
green (MG) and indigo carmine (IC) showed a maximum netic C o/C microrods to adsorb triphenylmethane dyes
adsorption of 274.4 and 135 mg/g on amine-functionalized
Table 2 Magnetic MOFs employed for dye adsorption

Magnetic MOF nanostructures Dye Maximum adsorption Remarks Ref.
ZIF-8@SiO2@MnFe2O4 Malachite green 1010.2 mg/g Response surface methodology (RSM) (Abdi et al. 2019)
Methyl orange 78.12 mg/g revealed the optimum conditions for maxi-
mum adsorption of dyes (0.005 g adsorbent
mass, 15 min of sonication, and 13 and
10 mg/L of initial dye concentration for
malachite green and methyl orange
3D stable pillared-layer MOF Rhodamine B 0.0042 mmol/g Adsorption of rhodamine B was faster than (Yang et al. 2017)
Methylene blue 0.0193 mmol/g MB. Synthesized MOF possess 6-con-
nected twofold interpenetrating frameworks
interacting by binuclear Cu (II) clusters
presenting pore selective separation
Fe3O4@MIL-100(Fe) Methylene blue 221 mg/g Electrostatic interactions and size filter effect (Aslam et al. 2017)
presented the efficiency
Fe3O4/MIL-101(Cr) Acid red 1 142.9 mg/g Monolayer adsorption with decreased entropy (Wang et al. 2016)
Orange G 200.0 mg/g is obtained
Fe3O4@MIL-100(Fe) AO 10 100% The core shell bio-nanocomposite was (Fan et al. 2018)
attached to the surface of bacteria via zero-
length cabodiimide strategy and was able
to remove dye by 100% through adsorption
and biodegradation
Fe3O4@MIL-100(Fe) Methyl red 625 mg/g The adsorption was greater than that of com- (Dadfarnia et al. 2015)
mercial activated charcoal, activated carbon,
and NaOH-modified activated carbon
13
Fig. 7 Synthesis of magnetic F

e3O4/Cu-BTC@Graphene with high-adsorption efficiency (adopted from Jabbari et al. (2016b))
due to the π-π interactions between Co/C microrods and frame work (MOF) prepared from dithizone-modified Fe3O4
sp2 graphitic carbon (Ye et al. 2019). nanoparticles and a copper-(benzene-1,3,5-tricarboxylate)
Functionalization to magnetic MOFs is another way MOF and its use in the preconcentration of Cd(II), Pb(II),
of increasing its dye adsorption capacity. F e 3O 4-based Ni(II), and Zn(II) ions. The limits of detection are 0.12,
Zr-based MOF (UiO-66) was functionalized with 0.39, 0.98, and 1.2 ng mL−1 for Cd(II), Zn(II), Ni(II), and
poly(propyleneimine) dendrimer (Far et al. 2020). Though Pb(II) ions, respectively. Ricco et al. (2015) have developed
the adsorption isotherms and kinetic models were well magnetic nanoparticles based on an aluminium MOF (MIL-
investigated and explained, the actual role of dendrimer in 53) and iron oxide nanoparticles for the uptake of lead(II)
enhancing the adsorption efficiency of magnetic Zr based ions. The iron oxide and aluminium based MOF depicted
MOF remain unexplained. A composite with biomaterial Pb(II) ions uptake up to 492.4 mg/g of composite, where
such as eggshell membrane was also used to functionalise the MOF played important role in lead adsorption and mag-
the magnetic ZIF-67 MOF and remove basic red 18 (BR netic particles allowed quick collection of sorbent from
18) dye from aqueous solutions (Mahmoodi et al. 2019). solution. Chen et al. (2016) synthesized ZnO/ZnFe2O4/C
As a whole, the pore structure, morphology, surface area, adsorbent using MOF (FeIII-modified MOF-5). The ZnO/
and pore volume and the co-operation between MOF and ZnFe2O4/C showed Pb(II) adsorption of 344.83 mg g−1.
dye molecules influence the adsorption efficiency and The adsorption mechanism involves substitution of Zn(II)
could be improved by varying those properties. by Pb(II) on ZnO surface indicating ion exchange. Sohrabi
et al. (2013) developed Mg-MOF using F e3O4-pyridine con-
Adsorption of heavy metal ions jugate and copper(II) complex of trimesic acid and studied
for Cd(II) and Pb(II) ions preconcentration. The Mg-MOF
Heavy (high density) metal ions are toxic chemicals present showed limit of detection of 0.2 for Cd(II) and 1.1 μgL − 1
in water, which are poisonous even at low concentration and for Pb(II) ions. Ahmadijokani et al. (2021) prepared ethylen-
dangerous to human health, therefore necessary to remove. ediamine-functionalized Zr-based metal–organic framework
Taghizadeh et al. (2013) developed magnetic metal–organic (MOF, UiO-66-EDA) through Michael addition reaction and
13
studied for Pb(II), Cd(II), and Cu(II) ions adsorption and which showed preconcentration of Co(II), Cu(II), Pb(II),
revealed adsorption follows pseudo-second-order kinetics Cd(II), Ni(II), Cr(III), and Mn(II) in aqueous solutions.
(Fig. 8). The Fe3O4@TMU-8 showed preconcentration in the range
Wang et al. (2017) developed magnetic cellulose between 66 and 232 with detection limits as low as 0.3 to
nanocrystal/MOF (Zn(II) and benzene-1,3,5-tricarboxylic 1 μg ⋅L−1. The high-adsorption capacity is attributed to the
acid) composite (MCNC@Zn-BTC) for removal of Pb(II) presence of azine group in MOF, which increases the heavy
from water. The adsorption process follows pseudo-second- metal ion adsorption. Huang et al. (2018) have developed
order kinetics. Abdollahi et al. (2020) developed F e 3O 4@ Fe3O4@SiO2@UiO-66 (Zr-MOF) and its amine derivatives
TMU-32 MOF-based nanocomposite by pore functionaliza- Fe3O4@SiO2@UiO-66-NH2 and Fe3O4@SiO2@UiO-66-
tion and surface charge modulation method. The F e 3O 4@ Urea, which shows significant adsorption efficiency for
TMU-32 nanocomposite shows enhanced removal capacity metal ions and organic dyes in aqueous solution. The amine-
for Pb(II) and Hg(II) ascribed to negative charge, modu- functionalized MOF shows high-adsorption efficiency for
lated surface in addition to homogeneous distribution of urea Pb2+ (102 mg g−1) and methylene blue (128 mg g−1). Song
and presence of Fe–O guest adsorptive sites contributing to et al. ( 2015) reported preparation of Ni@C nanocomposites
electrostatic interaction as the mechanism for heavy metal by calcining Ni3(OH)2(C8H4O4)2(H2O)4), which represented
ion removal. Ke et al. (2017) reported a thiol-functional- high-adsorption efficiency for rhodamine B is 84.5 mg g−1.
ized Fe3O4@MOF (Fe3O4@Cu3(btc)2) for Hg2+ and Pb2+ The Ni@C showed adsorption capacity for P b2+, Cu2+,
removal, which exhibits high-adsorption efficiency attrib- and Cd with 92.5 mg g , 63.4 mg g , and 41.4 mg g−1
2+ −1 −1
uted to thiol-functionalized MOF shell and magnetic mate- and removal efficiency of them are 92%, 70%, and 56%.
rial shows efficient separation of heavy metal ions (Fig. 9). The Ni@C shows strong magnetism and can be removed
Mahmoodi et al. (2019) reported ZIF-67@ F e 3O 4@ magnetically. Lv et al. (2019) reported synthesis of highly
ESM composite which showed adsorption capacity of magnetic NiO/Ni@C composites derived through pyrolyz-
344.82 mg/g for C u2+ and 250.81 mg/g for BR18. Roud- ing MOF which showed adsorption efficiency for arsenic(V)
bari et al. (2021) reported ZIF-8@SnO2@CoFe2O4 for Ni2+ (As(V)) 454.94 mg/g in aqueous solutions ascribed to rich
adsorption, which showed maximum adsorption capac- oxygen-containing functional groups and high-specific
ity of 21.43 mg g−1 and the adsorption kinetics followed surface area. Zhang et al. (2022b) prepared magnetic MIL-
the pseudo-first-order model. Safari et al. (2017) prepared 68(Ga) which showed adsorption efficiency for Pb2+ and
Fe3O4@TMU-8 magnetic MOF core–shell nanocomposite Cu2+ of 220 and 130 mg/g, respectively. Alqadami et al.
Fig. 8 Schematic of the influ-

ence of solution pH on the
surface charge of UiO-66-EDA
(Ahmadijokani et al. 2021)
Fig. 9 A Schematic of Fe3O4@MOF core–shell preparation. b Magnetic hysteresis loop of core–shell MOF
13
(2017) prepared Fe3O4@AMCA-MIL53(Al) composite and Cd(II), Pb(II), Co(II), and Ni(II) ions, respectively (Babaza-
studied for removal of U(VI) and Th(IV) from aqueous sys- deh et al. 2015b). Furthering their research, they looked
tem. The composite showed a adsorption capacity of 227.3 at how well [(Fe3O4-2,5-dimercapto-1,3,4-thiadiazole)/
and 285.7 mg/g for U(VI) and Th(IV), respectively, with Cu3(benzene-1,3,5-tricarboxylate)2] preconcentrated trace
endothermic and spontaneous adsorption. The adsorbed ions levels of Cd(II), Pb(II), and Zn(II) ions in baby food. Cd(II),
were easily recovered by desorption in 0.01 M HCl (Fig. 10). Pb(II), and Zn(II) each had a sorbent capacity of 155 mg g−1,
Magnetic MOFs nanocomposite was reported by Hassan- 173 mg g−1, and 190 mg g−1, respectively (Ghorbani-Kalhor
pour et al. (Babazadeh et al. 2015a) to extract trace levels of et al. 2015). Through the different studies, they were able to
heavy metal ions from agricultural samples. To preconcen- convincingly demonstrate that the magnetic nanocomposite
trate the trace amounts of Cd(II), Pb(II), Zn(II), and Cr(III) has benefits over other solid phases, including high enrich-
ions, they created a new magnetic MOF framework consist- ment factor, low limit of detection, and high enrichment
ing of (Fe3O4-ethylenediamine)/MIL-101(Fe). For cadmium, capacity. The method’s greater surface area and reduced
lead, zinc, and chromium, [(Fe3O4-ethylenediamine)/MIL- time need from the magnetically assisted separation of the
101(Fe)] had sorption capacities of 155 mg g−1, 198 mg g−1, adsorbent are additional benefits. The magnetic nanocom-
164 mg g−1, and 173 mg g−1, respectively. Another mag- posite can quantify the trace concentrations of heavy metals
netic MOF-based nanocomposite [(Fe3O4-dipyridylamine)/ at ng mL−1 levels in high-volume samples because of the
MIL-101(Fe)] was described in their other study, and it relatively high preconcentration factor (Table 3).
was used to preconcentrate trace levels of Cd(II), Pb(II),
Co(II), and Ni(II) ions in fish samples. With the limits of
detection reported to be 0.13, 0.75, 0.3, and 0.5 n gmL−1 for
Fig. 10 Synthesis of F
e3O4@AMCA-MIL53(Al) nanocomposite and its adsorption − desorption behavior for metal ions
13
Conclusion and Future perspectives demonstrated effective adsorption capabilities, address-

ing the challenges posed by various types of dyes. These
Magnetic metal–organic frameworks (Mg-MOFs) hold great materials hold promise for efficient water remediation.
promise for various applications, including catalysis, water • The use of MOFs and their carbon hybrids with mag-
treatment, dye removal, and the elimination of heavy metal netic properties holds great promise for addressing the
ions. Mg-MOFs, in particular, exhibit well-defined crys- challenges of dye removal from water. The integration of
talline porosity and flexibility. Their magnetic properties DFT calculations has provided valuable insights into the
enable the easy retrieval of composite catalysts from sys- molecular interactions between dyes and MOFs, enhanc-
tems. However, the choice of synthesis method depends on ing our understanding of the adsorption mechanisms.
specific goals, such as controlling size, enhancing magnetic • Additionally, the combination of MOFs with carbon
properties, or enabling functionalization, making it crucial materials such as graphene, graphene oxide, reduced
to select the appropriate approach for the desired applica- graphene oxide, and carbon nanotubes has yielded
tion of magnetic MOFs. Each method contributes to the hybrid structures with enhanced adsorption efficiency.
expanding versatility and potential of MOF-based magnetic These carbon hybrids not only improve dispersion within
nanomaterials across numerous fields, from environmental MOF’s but also offer the advantage of creating platforms
remediation to biomedicine. with small pores and diverse morphologies, further
enhancing their dye adsorption capabilities.
• The development of magnetic composites based on • The development of MOF-based materials with tailored
MOFs for photocatalytic degradation applications holds properties, such as surface modifications and function-
great promise. MOF-induced magnetic nanoparticles alization, has led to enhanced adsorption capacities and
have shown remarkable efficiency in the degradation of selectivity for specific metal ions. Additionally, the inclu-
various organic contaminants in aquatic environments. sion of magnetic components in these materials enables
• MOF-based materials, such as F e3O4/MIL-101, Fe3O4@ efficiency separation and recovery from aqueous solu-
SiO2@UiO-67, and ZIF-8 with magnetic F e2O3, have tions, making them highly practical for water treatment
demonstrated remarkable efficiency in adsorbing and applications.
removing various organic pollutants from water. Their
high-adsorption capacities, reusability, and ease of recov- Overall, the future of MOF-based magnetic composites
ery with magnets make them promising candidates for in various applications looks promising, with opportuni-
water treatment. Additionally, MOFs have shown poten- ties for innovation and optimization in materials and meth-
tial for simultaneous adsorption, detection, and removal odologies to enhance their efficiency and environmental
of pollutants, facilitating water quality monitoring and impact. However, several avenues for future research and
wastewater treatment. improvement can be explored.
• In the context of dye removal, MOFs like Fe3O4@ZTB-1,
Fe3O4@MIL-101, Cu3(BTC)2, and magnetic ZIF-67 have • Firstly, addressing the recombination of photo-induced
charge carriers in photo-degradation processes remains
Table 3 Different magnetic MOF materials for adsorption of heavy metal ions
Mg-MOF material Heavy metal ions Adsorption efficiency Reference
UiO-66-EDA Pb(II), Cd(II), and Cu(II) metal ions 243.90, 217.39, and 208.33 mg/g (Ahmadijokani et al. 2021)
(CNC@Zn-BTC) Pb(II) 558.66 mg/g (Wang et al. 2017)
Fe3O4@TMU-32 Hg(II) and Pb(II) 905 mg g−1, 1600 mg g−1 (Abdollahi et al. 2020)
thiol-functionalized Fe3O4@Cu3(btc)2 Hg2+ and Pb2+ - (Ke et al. 2017)
ZIF-67@ Fe3O4@ESM Cu2+, Basic Red 18 344.82 and 250.81 mg/g (Mahmoodi et al. 2019)
ZIF-8@SnO2@CoFe2O4 Ni2+ 21.43 mg g−1 (Roudbari et al. 2021)
Fe3O4@TMU-8 Co(II), Cu(II), Pb(II), Cd(II), Ni(II), LOD: 0.3–1 µg/L (Safari et al. 2017)
Cr(III), and Mn(II)
Fe3O4@SiO2@UiO-66-NH2 Pb2+ and methylene blue 102 mg g−1 (Huang et al. 2018)
128 mg g−1
Ni@C Pb2+, Cu2+, and Cd2+ with 92.5, 63.4, and 41.4 mg g − 1 (Song et al. 2015)
NiO/Ni@C As(V) 454.94 mg/g (Lv et al. 2019)
Fe3O4@AMCA-MIL53(Al) U(VI) and Th(IV) 227.3 and 285.7 mg/g (Alqadami et al. 2017)
13
a crucial challenge. The incorporation of intermediate Consent to participate All the authors agree to participate and have
layers such as SiO2, H2O2, or graphene oxide (GO) has contributed to the review article.
shown promise in mitigating charge carrier recombination Consent for publication All the authors agree to submit the review
and improving photocatalytic efficiency. Further research article to Environmental Science and Pollution Research.
into optimizing these intermediate layers and exploring
new materials could enhance the overall performance of Competing interests The authors declare no competing interests.
MOF-based photocatalysts. Additionally, the creation of
core–shell heterostructure, where MOF shells encapsu-
late magnetic nanoparticles, has the potential to improve
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Recent Advances in Metal Organic Frameworks-Based Magnetic Nanomaterials For Waste Water Treatment

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Recent Advances in Metal Organic Frameworks-Based Magnetic Nanomaterials For Waste Water Treatment

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Environmental Science and Pollution Research

Recent advances in metal organic frameworks–based magnetic

Received: 31 May 2023 / Accepted: 17 November 2023

Keywords Magnetic nanoparticles · MOF · Fe · Water treatment · Adsorption · Degradation

Introduction environment is critical for ensuring a healthy and sustain-

Fig. 1 Graphical representation

sonochemical, flow chemistry, solvothermal, dry-gel, Solvo(hydro)‑thermal and iono‑thermal method

Fig. 3 Schematic representation

Template strategies Photocatalytic degradation is considered one of the prom-

Fe3O4@MIL-53(Fe) Ibuprofen 99 60 10 400 (Ning Liu 2020)

Fig. 5 A Adsorption mechanism

Fig. 6 Mechanism of adsorption

Table 2 Magnetic MOFs employed for dye adsorption

Fig. 7 Synthesis of magnetic F

Fig. 8 Schematic of the influ-

Conclusion and Future perspectives demonstrated effective adsorption capabilities, address-

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