Journal of Industrial and Engineering Chemistry 103 (2021) 292–304

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Manganese ferrite (MnFe2O4) Nanoparticles: From synthesis to

application -A review
Neda Akhlaghi, Ghasem Najafpour-Darzi ⇑
Biotechnology Research Laboratory, Faculty of Chemical Engineering, Babol Noshirvani University of Technolgy, Shariati Avenue, Babol 47148-71167, Iran

a r t i c l e i n f o a b s t r a c t

Article history: Manganese ferrite (MnFe2O4) nanoparticle, a spinel ferrite nanomaterial, is one of the important mag-
Received 22 June 2021 netic metal oxide nanoparticles with distinctive physical and chemical properties. This nanoparticle
Revised 20 July 2021 can be easily synthesized through various methods with controllable size and desired morphology.
Accepted 26 July 2021
MnFe2O4 is an efficient candidate for various applications like biomedical, analytical, and storage devices.
Available online 2 August 2021
In this review, several synthesis methods and physicochemical properties of MnFe2O4 nanoparticles are
discussed. Then, a comprehensive overview of the latest and most promising researches on massive
Keywords:
applications of MnFe2O4-based nanostructures, including hyperthermia cancer therapy, magnetic reso-
MnFe2O4 nanoparticles
Electrochemical sensors
nance imaging (MRI), energy conversion and storage devices like Lithium-ion batteries and supercapac-
Hyperthermia itors, as well as catalytic activities, sensors, hydrogen production, heavy metal removal, and drug delivery
Supercapacitors are presented. Overall, herein, a deep understanding of the unlimited ability of MnFe2O4 nanoparticles in
Lithium-ion batteries diverse applications is provided.
Ó 2021 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction low degree of inversion can result in the formation of MnFe2O4

Nanoparticles (NPs) are submicron molecules composed of
organic or inorganic materials. Owing to size-dependent proper-
ties, NPs demonstrate new or improved characteristics in compar-
ison to bulk materials which lead to novel applications [1,2].
Considering the broad range of materials that have been used in
preparation of NPs, they can be classified as metallic NPs, metal
and non-metal oxides NPs, semiconductor NPs, and carbon NPs
[3]. In metal oxide NPs, MnFe2O4 is one of the promising and inter-
esting spinel ferrite NPs which combined the advantages of both
Fe-and Mn-based materials [4].
The MnFe2O4 NPs exhibited mixed spinel structure (Fig. 1),
where metal cations Mn2+ and Fe3+ are fitted at A (tetrahedral)
and B (octahedral) sites, formed by face-centered close packing
arrangement of oxygen anions [Mn2þ 3þ 2þ 3þ
1i Fei ]A [Mni Fe2i ]B O4 [4,5].
In this formula, i is known as inversion parameter and referees to
the inversion degree. In normal spinels (i = 0), all of the Mn cations
are in tetrahedral sites, while in inverse spinels (i = 1) they occupy
the octahedral sites [5]. Notably, the magnetic properties of
MnFe2O4 NPs, like magnetization, anisotropy, and Neel tempera-
ture are correlated to the inversion degree [4,5]. In other words,
⇑ Corresponding author at: Tel.: +98 11 32310975.
E-mail address: najafpour@nit.ac.ir (G. Najafpour-Darzi).
NPs with high magnetization [5]. This fact, inversion degree, is
attributed to the synthesis methods, especially different annealing
temperatures and rates of cooling [6].
The MnFe2O4 demonstrated higher biocompatibility in compare
to hematite, cobalt ferrite, magnetite, and nickel ferrite; which
make it an efficient candidate for various biomedical applications
such as drug delivery and magnetic resonance imaging (MRI)
[7,8]. In addition, MnFe2O4 NPs have been recognized as heater
source in magnetic hyperthermia-mediated cancer therapy due
to production of heat under alternating magnetic fields [9]. The
heating efficiency of MnFe2O4 NPs under oscillating magnetic field
strongly related to the saturation magnetization of NPs, which is
closely influenced by the particles size, shape, and the cation distri-
bution within the tetrahedral and octahedral sites. These charac-
teristics can be controlled by the applied synthesis methods and
conditions [10].
Furthermore, the MnFe2O4 nanoparticle has attracted immense
interest in electronic systems owing to soft-magnetic properties
characterized by low coercivity, high magnetic permeability, and
moderate saturation magnetization [5]. Superparamagnetic nature,
simple preparation, high chemical stability, high electric resistiv-
ity, and high crystal symmetry are other well-known advantages
of MnFe2O4 NPs [5,7].

https://doi.org/10.1016/j.jiec.2021.07.043
1226-086X/Ó 2021 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
N. Akhlaghi and G. Najafpour-Darzi Journal of Industrial and Engineering Chemistry 103 (2021) 292–304

the formation of more uniform MnFe2O4 NPs with lower crystallite

Fig. 1. Crystal structure of MnFe2O4 NPs. The Fe3+ cations are located in octahedral
sites and hexa-coordinated with oxygen anions, whereas the Mn2+ cations are
located in tetrahedral sites.
In spite of the valuable properties and importance of MnFe2O4
NPs, a comprehensive review on MnFe2O4-based nanostructures
has not yet been published. To the authors’ best of knowledge, only
one review article allocated to manganese ferrites NPs which
focused on magnetic resonance imaging (MRI) application [11].
Hence, in this review, the most recent studies on MnFe2O4 NPs
were discussed. After a brief review on preparation methods and
evaluating influential parameters on physicochemical properties
of MnFe2O4 NPs, we focused on main potential applications of
MnFe2O4-based nanostructures including biomedical, analytical,
fuel production, storage devices, removal of heavy metals, and cat-
alytic activities as well.
Synthesis and properties of MnFe2O4 NPs
In the past decade, MnFe2O4 with different physicochemical
properties have been synthesized through various methods (see
Table 1). The most common of which include solvothermal
[5,12–15], hydrothermal [16–20], sol-gel [21,22], co-precipitation
[23–31], thermal decomposition [32,33], solution combustion
[34], micro-emulsion [8], polyol [35], spray pyrolysis [36],
template-synthesis [37], microwave-induced combustion [38],
sonochemical [39,40], and physical solid state methods [41]. The
physical properties of MnFe2O4 NPs can be controlled by the selec-
tion of an appropriate synthesis method. Asghar et al. [7] revealed
size through thermal decomposition method (5 nm) in compare to
that obtained by the co-precipitation method (9.5 nm).
Operation parameter also affected the physical characteristics
of MnFe2O4 NPs. Wang et al. [42] reported formation of plate-like
shape, spherical, and near cubic MnFe2O4 NPs with average TEM
size of 18, 16, and 27 nm, respectively, by changing the amounts
of Fe(acac)3 and Mn(acac)2 as precursors in oleic acid. The adsorp-
tion of different amount of capping agent on different free surface
energy is demonstrated to be responsible for the synthesis of
MnFe2O4 NPs with various shapes and sizes [42].
The effect of pH on saturation magnetization of MnFe2O4 NPs
has been evaluated by Iranmanesh et al. [43] in the co-
precipitation synthesis method. The literature results revealed a
decrease in saturation magnetization of the synthesized NPs from
66.4 to 60.8 emu/g by increasing the pH value from 9 to 11, respec-
tively. In other words, the formation of small size NPs at high pH
caused a reduction in saturation magnetization of the sample.
Another important synthesizing parameter is reaction tempera-
ture. High crystalline and pure MnFe2O4 NPs were obtained at
hydrothermal reaction temperature of 200°C in comparison to
low reaction temperature of 140°C [18]. A comparative study on
reaction time has been conducted by Yadav et al. [39]. Experiments
were performed to evaluate the effect of sonication time on the
crystallite size, saturation magnetization, and conductivity of
MnFe2O4 NPs synthesized through sonochemical method. The
obtained results indicated that the crystallite size, and saturation
magnetization of the prepared NPs increased from 1.8 nm and
1.9 emu/g to 22.1 nm and 52.5 emu/g with increasing the sonica-
tion time from 20 to 80 min, respectively. Meanwhile, the conduc-
tivity of the synthesized MnFe2O4 NPs at sonication time of 80 min
was lower (3.1109 S/cm) in comparison to that synthesized at
sonication time of 20 min (368109 S/cm).
Taken together, the selected synthesis method and the opera-
tion conditions affected the physicochemical characteristic of
MnFe2O4 NPs. Generally, high reaction temperature is in favor of
synthesis of the small size NPs; meanwhile, the saturation magne-
tization reduced for very small NPs. In fact, physicochemical prop-
erties of MnFe2O4 NPs strongly influenced by the size and
morphology of the prepared NPs. A suitable synthesis method at
optimum reaction conditions should be selected according to the
needs of application.
Applications of MnFe2O4 NPs
Based on recent literature review on MnFe2O4 NPs, the main
applications of MnFe2O4-based nanostructures are discussed in
the following sections (see Fig. 2).

Table 1
Comparison of physicochemical properties of MnFe2O4 NPs synthesized via different methods.

Synthesis method Temp. (°C) Time (h) Structure Size (nm) Ms (emu/g) Surface area (M2/g) Ref.
Polyol 210 3 Quasi-spherical 7 (DTEM) 51.99 165.39 [35]
Co-precipitation 70 2 Cubic 20–80 (DSEM) 61.39 84.5 [30]
Co-precipitation 95 2 Cubic 30 (DTEM) 56 - [28]
Thermal decomposition 295 1 Spherical 7 (DTEM) 39 - [32]
Thermal decomposition 270 1.5 Spherical 18.9 (DSEM) - - [33]
Solution combustion 300 - Spherical 30–35 (DSEM) 46 33 [34]
Hydrothermal 200 12 Quasi-spherical 30–50 (DTEM) - - [18]
Hydrothermal 220 10 Spherical 14.5 (DTEM) - - [17]
Hydrothermal 180 28 Hollow microsphere 280 (DTEM) 49.7 32.19 [20]
Solvothermal 200 12 Spherical CNAs 230 (DTEM) 61.6 60.2 [12]
Solvothermal 200 24 Cubic 8.6 (DTEM) 54.6 - [5]
Solvothermal 180 12 Nearly spherical 60 (DSEM) 43.3 70 [14]

Abbreviation: Ms: saturation magnetization; CNAs: colloidal nanocrystal assemblies.

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N. Akhlaghi and G. Najafpour-Darzi
Fig. 2. Applications of MnFe2O4 NPs in various scientific fields.
Magnetic hyperthermia
In magnetic hyperthermia, the magnetic NPs induce local heat
under an external alternating magnetic field where the tumor cells
are located [44]. Cancer cells are sensitive toward heat because of
poor blood flow and consequently insufficient oxygen around
them; whereas, healthy cells possess the capability to dissipate
additional heat in their region through conduction and convection
phenomena by systematically organization of blood flow [45]. In
this treatment technique, the mechanism of heat generation by
magnetic NPs is through various magnetization reversal processes
including hysteresis and Neel or Brown relaxation [25,44,46].
A key parameter for evaluating the heating efficiency of mag-
netic NPs is specific absorption rate (SAR). Different reported SAR
values of MnFe2O4-based nanostructures are summarized in
Table 2. This parameter is influenced by the size, concentration,
and shape of NPs, as well as applied frequency and magnetic field.
Iqbal et al. [46] demonstrated concentration dependency of the
SAR. Their experiment revealed that decrease in the SAR values
from 84.65 W/g to 67.62, 58.8, 55, 53.45, and 47.84 W/g by increas-
ing the concentration of MnFe2O4 NPs from 0.9 mg/mL to 1.3, 1.7,
2.2, 2.6, and 3.5 mg/mL, respectively. The decrease in SAR with
increasing NPs concentration is likely to be caused by an increase
in the dipolar magnetic moment at high concentration of MnFe2O4
NPs, which affected the time of Neel relaxation [46].
Hyperthermia efficiency of magnetic NPs is influenced by the
size of NPs. As the size of NPs increased the saturation magnetiza-
tion will increase which is suitable for hyperthermia applications
[47]. No hyperthermia effect was observed using too small NPs
[47]. In fact, at NPs size below 5 nm some disorders occur on the
surface spin of NPs which lead to reduction in magnetization
[45]. On the contrary, too big particles faced to problem of NPs fil-
tration by Kupffer cells of liver [25]. Mondal et al. [24] revealed
enhancement of heating efficiency of MnFe2O4/ZnS nanocompos-
ites in compare to bare MnFe2O4 NPs owing to increase in the size
and dynamic magnetization of the nanocomposites.
In hyperthermia, the malignant tissues were demolished or
became more susceptible to the effects of anticancer drugs when
exposed to high temperatures (approximately 42°C); meanwhile,
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Journal of Industrial and Engineering Chemistry 103 (2021) 292–304
at temperature of higher than 46°C the normal surrounding tissues
will be damaged [46]. So, controlling the temperature near to 42°C
is critical in this technique. Iqbal et al. [46] reported that the
desired saturation temperature of 42°C can be achieved by chang-
ing either the concentration of MnFe2O4 NPs or the strength of the
magnetic field. At fixed magnetic field strength, the saturation
temperature increased by an increase in the concentration of
NPs, since at high concentration more NPs as heat generators are
present in the solution. Moreover, at a fixed concentration, the sat-
uration temperature of MnFe2O4 NPs increased/or decreased by
adjusting higher/or lower field strength.
In short, too small size MnFe2O4 NPs are not suitable for hyper-
thermia therapy. For this treatment approach, it is advantageous to
have desired temperature which is required for the cancer cell
ablation with as low as possible number of the required NPs with
high saturation magnetization. The performance of MnFe2O4 NPs
as heat generator can be controlled in different biological environ-
ment by adjusting either the magnetic field strength or the concen-
tration of NPs.
Magnetic resonance imaging (MRI)
MRI as a powerful imaging tool is widely used in medical diag-
nosis [51]. In this technique, images are produced based on the
relaxation properties of water proton (hydrogen) nuclei in the local
tissue [52,53]. However, the major drawback of MRI technique is
low signal sensitivity which required the administration of large
quantities of contrast agents for enhancing image contrast
between biological tissues [53]. Magnetic NPs are potential candi-
date of contrast agent for increasing the probe sensitivity owing to
their magnetization properties and long circulation times [32,54].
The efficiency of magnetic NPs as a contrast agent in MRI appli-
cation is evaluated based on transverse relaxivity (r2), which is cal-
culated from the slope of a plot of 1/T2 versus concentration. Spin-
spin relaxation time (T2) also known as T2 relaxation; which is a
phenomenon that is attributed to the molecular interactions
through the process of transverse relaxation [55]. Generally, the
rate of relaxation should be high enough for having low signal
intensity (high negative contrast) [53].
N. Akhlaghi and G. Najafpour-Darzi Journal of Industrial and Engineering Chemistry 103 (2021) 292–304

Table 2
Comparison of heating efficiency of MnFe2O4 NPs in hyperthermia.

Material Synthesis method Conc. (mg/mL) Size (nm) DTEM Ms (emu/g) SAR (W/g) Frequency (kHz) Ref.
MnFe2O4 Co-precipitation 2 6–6.5 0.311 27.66 336 [4]
MnFe2O4 Co-precipitation 8 6–6.5 0.311 7.14 336 [4]
MnFe2O4 Co-precipitation 10 19 68.8 148.4 1950 [48]
MnFe2O4 Co-precipitation 400 25 54.18 217.62 280 [9]
MnFe2O4 Polyol 4 83 76 965 355 [49]
MnFe2O4/SiO2 Reverse micelle 0.9 14 38 84.65 355 [46]
MnFe2O4/ZnS Co-precipitation 2 40–50 1.15 29.33 260 [24]
MnFe2O4/CS SMG 7 18.3 31.2 1.08 266 [50]

Abbreviation: CS: chitosan; SMG: seed mediated growth.

Mn-ferrite-based oxides NPs are widely used as T2 contrast
agents and were demonstrated to be more efficient in enhancing
transverse relaxivity (r2) in compare to iron oxides [11]. In this
context, MnFe2O4 NPs possess very high saturation magnetization
and excellent T2-negative contrast [11,32,56]. Table 3 summarizes
results of transverse relaxivity (r2) of various MnFe2O4-based
nanostructures with different sizes and magnetization. Wang
et al. [42] revealed that the T2-weighted signal intensity decreased
with an increase in the size of MnFe2O4 NPs. Li el al. [56] observed
an increase in both longitudinal and transverse relaxivities of
MnFe2O4 NPs with an increase in particle size due to most likely
to an increase in magnetization. Based on the reported data, mag-
netization increased from 0.22 emu/g to 0.44, 1.06, 9.49, and
11.6 emu/g with an increase in MnFe2O4 NPs size from 2.2 nm to
2.4, 2.6, 3.3, and 4.9 nm, respectively. In other words, large NPs size
with high magnetization exhibited high transverse relaxivity (r2)
due to reduced spin-canting effect [11].
The value of proton relaxivity can be improved in MRI imaging
by appropriate surface coating. Coating has direct influence on
magnetic field inhomogeneity spreading around the nanostructure,
interactions between magnetic center and water protons, and
magnetization of NPs through effecting on the arrangement of sur-
face atoms [57]. To maintain high r2values, thin coating is neces-
sary to reduce the distance between water molecules and
magnetic core [57]. In addition, high hydrated surface and fast
water exchange rate are critical for appropriate surface coating in
MRI imaging [57]. Venkatesha et al. [51] revealed that the trans-
verse relaxivity of water protons in the dispersion of MnFe2O4-
Fe3O4 core–shell NPs (Ms: 69.34 emu/g, size: 12.5 nm, r2:
184.1 m/Ms) was significantly enhanced in compare to MnFe2O4
NPs (Ms: 61.5 emu/g, size: 9 nm, r2: 83.2 m/Ms) and Fe3O4 NPs
(Ms: 65.8 emu/g, size: 12 nm, r2: 96.6 m/Ms) due to greater mag-
netic inhomogeneity created by the magnetic core–shell NPs which
increased proton relaxivity value.
Generally, the ability of MnFe2O4 to reduce T2 relaxation time
and increase in the transverse relaxivity (r2) of the hydrogen nuclei
in the specific tissues is suitable for application of this nanoparticle
as MRI contrast agents. High relaxivity values can be obtained use
of larger size NPs owing to direct correlation between the particle
size and its saturation magnetization.
Lithium-ion batteries
Lithium-ion batteries (LIBs) as energy storage devices are
widely used in portable electronic devices and all types of electric
vehicles owing to stable power output, high energy density, and
long cycle life [60,61]. Graphite is the typical anode material for
commercial LIBs, suffering from low theoretical capacity (372
mAh/g) [20,60]. MnFe2O4 as binary transition metal oxides pos-
sesses theoretical capacity of 926 mAh/g which is much higher
than that of graphite [62]. In addition to high theoretical capacity,
advantages like low cost, environmental friendliness, and low
intercalation potential for Lithium ions make MnFe2O4 a promising
anode material for LIBs [62,63]. A schematic illustration of working
mechanism of LIB using MnFe2O4NPs is illustrated in Fig. 3.
According to Eq. (1), the electrochemical reaction of MnFe2O4 at
anode after the first discharge involves Li uptake along with
decomposition of MnFe2O4 into its metallic states (Mn/Fe) and
generation of amorphous Li2O [63,64]:
þ
MnFe2 O4 þ 8Li þ 8e ! Mn þ 2Fe þ 4Li2 O ð1Þ
Then, MnO and Fe2O3 formed through the following reversible
reaction [63]:
þ
Mn þ 2Fe þ 4Li2 O ! MnO þ Fe2 O3 þ 8Li þ 8e ð2Þ
Although, small size of MnFe2O4 NPs could facilitate high rate
Li-ion diffusion in electrochemical processes [65]; nevertheless,
poor electronic conductivity and drastic volume change during
charge/discharge processes led to poor cyclic stability and large
irreversible capacity [65–67]. To overcome such problems, com-
posite electrodes using carbonaceous components like amorphous
carbon and graphene were used (Table 4). Li et al. [66] revealed
that encapsulation of MnFe2O4 NPs into carbon framework, derived
from the pyrolysis of nitrilotriacetic acid (NTA), increased the con-
ductivity of anode material and improved electron conduction. In

Table 3
Comparison of transverse relaxivity (r2) of MnFe2O4-based nanostructures.

Material Synthesis method Size (nm) DTEM Ms (emu/g) r2 (m/Ms) Ref.

MnFe2O4/Fe3O4/CS Thermal decomposition 12.5 69.34 184.1 [51]
MnFe2O4/CS Thermal decomposition 9 61.5 83.2 [51]
MnFe2O4 Thermal decomposition 7 39 189.3 [32]
MnFe2O4/PEG Modified reductive protocol 6.4 33.7 118 [58]
MnFe2O4/mPEG Thermal decomposition 6 41.5 75.7 [59]
MnFe2O4/mPEG-g-PEI Thermal decomposition 6 40.6 331.8 [59]
MnFe2O4/Oleic acid Thermal decomposition 18 54.67 53.13 [42]
MnFe2O4/CTAB Solvothermal 8.6 54.6 196.6 [5]
MnFe2O4/PMAA-PTMP Co-precipitation 2.2 0.22 6.61 [56]

Abbreviation: CS: chitosan; CTAB: cetyltrimethylammonium bromide; PMAA-PTMP: Poly (methacrylic acid) pentaerythritol tetrakis (3-mercaptopropionate); PEG: poly
(ethylene glycol); mPEG: methoxypoly (ethylene glycol); PEI: polyethylenimine.

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Fig. 3. Working principles of LIB using MnFe2O4 as anode material.

addition to electronic conductivity improvement of electrode
materials, carbon shell coating on MnFe2O4 NPs could prevent
NPs agglomeration and provide a protective buffering layer that
is affected by pulverization of anode materials, resulted in cycling
stability [62]. Based on the literature results, the capacities of 850
and 550 mAh/g were reported using MnFe2O4 NPs core with a car-
bon outer shell after 400 and 1000 cycles, demonstrated long-term
cycling performance [66].
To take advantage of the carbonaceous materials, reduced gra-
phene oxide (rGO) has been used in combination with MnFe2O4
NPs for fabrication of high performance anode composites in LIBs
[64,65,68]. In fact, the dispersion of MnFe2O4 NPs on the rGO
sheets provides a specific structure that could suppress the aggre-
gation of NPs during long time cycling, provides a large specific
surface area, alleviates volumetric expansion during cycling, and
accelerates the transfer of Lithium-ion during lithiation/delithia-
tion process [63,65,69,70].
To improve the electrochemical performance of LIBs, meso-
porous and hollow structured MnFe2O4-based materials were
employed (Table 4). Use of mesoporous structure is beneficial for
reducing the volume expansion and developing passage of lithium
ions [60,66]. In addition, high electroactive sites are available using
porous and hollow structure MnFe2O4-based electrodes owing to
increasing surface area [20,71]. Also, the interior void space of hol-
low structure particles provided more Lithium-storage sites which
has a positive effect on high cycling stability [62].
Taken together, the chemical stability and conductivity of
MnFe2O4 NPs can be improved in design of high power LIBs, bene-
fiting from the synergistic effect of its porous structure and combi-
nation with carbonaceous materials. Application of porous carbon
materials provides high void space and electron conductivity,
which is vital to improve the performance of MnFe2O4-based
anodes materials.
Supercapacitor
Supercapacitors as flexible electrochemical capacitors are
important energy storage devices with potential applications in
portable and wearable systems [72]. Batteries have higher energy
density compared to capacitors, meanwhile when substantial
energy at high power is required, capacitors are suitable devices
[73].
Based on charge storage mechanism and electrode configura-
tion, supercapacitors can be classified into three groups namely
electric double layer capacitors (EDLCs), pseudocapacitors, and
hybrid supercapacitors [74]. EDLCs are based on carbonaceous
materials and stored energy through the accumulation of electro-
static charge at the interface of electrode/electrolyte, while in
pseudocapacitors, energy storage occurs through Faradaic reac-
tions or redox reactions on the surface of electrically conductive
polymers and metal oxides as electrode materials [74–76]. In
hybrid supercapacitors, the combination of both redox reaction
and EDLC is used for charge storage [75].
Hydrated amorphous ruthenium oxide (RuO2) is the first pseu-
docapacitive compound with high power density in acidic elec-
trolyte solutions; it is suffering from high cost [77]. Hydrated
amorphous manganese oxide (MnO2) as a low cost material was
discovered in late 90s as pseudocapacitance in neutral solutions;
nevertheless, the main obstacle of the application of MnO2 is its
poor cycling stability [77]. MnFe2O4 NPs can be used for the fabri-

Table 4
Electrochemical performance of MnFe2O4-based anodes materials in LIBs.

Anode material Structure Synthesis method Electrochemical properties Ref.

No. Cycles Cd (A/g) Rc (mAh/g)
MnFe2O4/C Hollow nanospheres Hydrothermal, in-situ carbonization, self-etching 60 0.2 973 [19]
MnFe2O4/C Hollow microspheres Emulsification, in-situ carbonization, annealing 300 2 730 [62]
MnFe2O4 Porous microrods Microemulsion, annealing 1000 1 630 [71]
MnFe2O4/GN Two-dimensional sandwich In-situ solvothermal 80 0.2 987.95 [63]
MnFe2O4/GN NPs decorated on sheet Hydrothermal 200 1 768 [67]
MnFe2O4/TiO2 Mesoporous spheres Co-precipitation, annealing 200 0.1 775 [69]
MnFe2O4/rGO NPs decorated on sheet In-situ co-precipitation 100 0.2 653.2 [65]
MnFe2O4/rGO NPs decorated on sheet In-situ co-precipitation 200 1 581.2 [68]

Abbreviation: Rc: reversible capacity; Cd: current density C: carbon; GN: graphene; rGO: reduced graphene oxide.

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cation of electrode materials in pseudocapacitors and hybrid
supercapacitors to improve redox reactions and provide superior
cycling stability in compare to conventional MnO2-based pseudo-
capacitive devices. Particularly interest in the application of
MnFe2O4 NPs in supercapacitors is due to their high pseudocapac-
itance, multi oxidation states, high power delivery, and high
cycling stability [74,76,78]. In fact, the use of MnFe2O4 NPs in elec-
trode material increases available active sites and also reduces the
path lengths of OH– ion diffusion [18].
The electrochemical performance of pseudocapacitor influenced
by the size of MnFe2O4 NPs. Guo et al. [79] used MnFe2O4 colloidal
nanocrystal assemblies (CNAs) as electrode material. In their work,
the size of the primary NPs in the as-made MnFe2O4 CNAs has been
increased from 16 nm to 43 nm, which has resulted in decrease in
the capacitance of supercapacitor from 88.4 to 20.2F/g (0.01 A/g),
respectively.
Semiconductive nature of MnFe2O4 [76] necessitated a combi-
nation of MnFe2O4 with various carbon-based active chemicals
(Table 5). Hence, owing to high electrical conductivities, car-
bonized organic resources are used in electrochemical application
[80]. Use of graphene and polyaniline as conductive materials for
construction of a ternary MnFe2O4/graphene/polyaniline hybrid
supercapacitor enhanced ions transfer into the electrode [74].
Thu et al. [75] reported fabrication of a ternary hybrid electrode
composed of polypyrrole shell, as a conductive polymer, and
reduced graphene oxide sheets decorated with MnFe2O4 micro-
spheres. Two-to three-fold increase in the specific capacitance of
supercapacitor was observed in compare to bare MnFe2O4 and
polypyrrole due to synergistic effects of hybrid composite that
reduced diffusion resistance.
In short, MnFe2O4 NPs as high pseudacapacitive material pro-
vide more active sites on the electrode which is suitable for ion
transfer. Synthesis of hybrid composites using MnFe2O4 NPs com-
bined with carbonaceous compounds opens promising direction
for fabrication of high performance charge storage devices due to
combination of the characteristics of both compounds and over-
coming their defects as electrode materials for application in
supercapacitors.
Catalyst
Advanced oxidation processes (AOPs) including catalytic ozona-
tion, electrochemical oxidation, photocatalytic oxidation, and Fen-
ton reaction are well known as effective treatment techniques for
decomposition of contaminants in a short time [86]. In AOPs, the
MnFe2O4 NPs as nanocatalysts have great potential to activate both
peroxymonosulfate (PMS) and H2O2 as oxidants to generate reac-
tive oxygen species (ROS) like SO .
4 and OH, respectively [87]
(see Fig. 4).
In fact, MnFe2O4 NPs benefited from the synergistic effect
between Fe and Mn ions to accelerate the generation of active rad-
icals [88]. The produced ROS by the catalytic activities of MnFe2O4
NPs are responsible for the degradation of dyes and drugs into less
harmful chemicals.
In the process of PMS activation, the Mn(II) species on the cat-
alyst surface can react with PMS to produce SO 4 and Mn(III). Sim-
ilarly, Fe(II) species located on catalyst surface with PMS will
produce SO 4 and Fe(III), as well. The produced Mn(III) and Fe(III)
species can then react with PMS to generate SO 5 [89]. Hence,
Mn(II)/Mn(III) and Fe(II)/Fe(III) as redox couples reacted with
PMS for production of free radical, performed a Fenton-like system.
The conventional Fenton process, as one of the classical and
popular AOPs [22,90], carried out at acidic condition (pH 2–3);
while, Fenton-like system using MnFe2O4-based nanostructures
as catalysts performed degradation or removal of contaminants
at neutral pH, which is more desired [16,22,88,91]. At high pH
(above 9.5), Mn2+ ion may participate in the chain reaction to form
HO2 =O
2 instead of hydroxyl radicals generation [87]. Instability of
H2O2 along with the formation of undesired ferric hydroxide com-
plexes at high pH, reduced dye degradation [13,87]. On the other
hand, in extreme acidic condition, the generation of ROS reduced
because of the high stability of PMS at very low pH values which
prevents the degradation process [92]. Therefore, MnFe2O4 NPs
as nanocatalysts are active at neutral pH.
As a typical metal oxide NPs, the MnFe2O4 strongly tend to
aggregate because of high surface energy. The aggregated NPs have
low accessible specific surface area, which limits their catalytic
performance in activation of oxidants [88]. To overcome these
problem, various combinations of MnFe2O4 NPs with active mate-
rials have been used for the degradation of contaminates like dyes
and drugs (Table 6). Zhou et al. [88] reported fabrication of MnFe2-
O4 NPs attached to cellulose nanocrystals (CNC) for dye degrada-
tion. The MnFe2O4/CNC composite exhibited 60% increase in dye
degradation in comparison to bare NPs; that was due to 3.6 times
increase in NPs surface area. Another work conducted by Yao et al.
[93] revealed the significant role of graphene in the improvement
of activity of MnFe2O4 NPs in activation of PMS species. A 10%
increase in dye degradation was observed by using MnFe2O4/re-
duced graphene oxide hybrid system compared to MnFe2O4 NPs.
The combination of MnFe2O4 with graphene oxide not only pro-
vided uniform dispersion of MnFe2O4 NPs on graphene surface
and prevented NPs aggregation, but also a synergistic function of
large surface area was available that improved chemical reaction
sites and electron transport ability [89].
Taken together, MnFe2O4-based nanostructures as Fe-
containing materials exhibited great catalytic activities toward
the treatment of non-biodegradable contaminates; especially, at
neutral pH which is more favorable for practical applications. Com-

Table 5
Electrochemical performance of MnFe2O4-based electrode materials in supercapacitor.

Material Structure Electrolyte Specific capacitance (F/g) Capacity retention Ref.

MnFe2O4 Nano-agglomeric 1 M KOH 1283 at (1 A/g) 94% after 5000 cycles [37]
MnFe2O4 Nanosphere 3.5 M KOH 245 at (0.2 A/g) 105% after 10,000 cycles [27]
MnFe2O4 Quasi-spherical 2 M KOH 282.4 at (0.5 A/g) 85.8% after 2000 cycles [18]
MnFe2O4/GN Microsphere coated on nanosheets PVA-H2SO4 gel 120 at (0.1 A/g) 105% after 5000 cycles [72]
MnFe2O4/GN NPs coated on nanosheets 1 M Na2SO4 50 at (0.5 A/g) 90% after 4500 cycles [81]
MnFe2O4/GN/PANI NPs coated on nanosheets 1 M KOH 454.8 at (0.2 A/g) 76.4% after 5000 cycles [82]
MnFe2O4/CB/PANI NPs coated on CB 0.5 M H2SO4 204.3 at (0.5 A/g) 80% after 10,000 cycles [83]
MnFe2O4/PANI NPs distributed in nanofibers 1 M H2SO4 371 at (1 A/g) 86.7% after 2000 cycles [78]
MnFe2O4/rGO NPs coated on flake-like sheets 6 M KOH 271 at (0.5 A/g) 104% after 5000 cycles [84]
MnFe2O4/CNF NPs distributed in carbonized fibers 2 M KOH 291.9 at (5 A/g) 80% after 1000 cycles [76]
MnFe2O4 CNAs Spherical 2 M KOH 56.2 at (2 A/g) 59.4% after 2000 cycles [79]
MnFe2O4/C Nanowires 2 M KOH 824 at (0.1 A/g) 93.9% after 10,000 cycles [85]

Abbreviation: GN: graphene; rGO: reduced graphene oxide; PANI: polyaniline; CNF: carbon nanofibers; CNAs: colloidal nanocrystal assemblies; C: carbon; CB: carbon black.

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N. Akhlaghi and G. Najafpour-Darzi Journal of Industrial and Engineering Chemistry 103 (2021) 292–304

Fig. 4. Possible mechanisms of H2O2 and PMS activation by MnFe2O4 NPs [16]

bination of MnFe2O4 NPs with hydrophilic compounds prevents
NPs to form aggregation; consequently, enhances available active
surface area for activation of oxidants.
Sensors
Metal oxides NPs with excellent catalytic activities impart a
novel area in electrochemical sensors. Use of modified electrodto
resolve es with NPs can enhance electron transfer between analyte
and electrode; thereby, the selectivity and sensitivity of the sensor
improved [35,96]. In comparison to bare iron oxide NPs, addition of
another element like Mn has a positive impact on increasing the
amount of released electron and consequently increasing the
adsorption of oxygen species [97]. In fact, both cations (Mn2+ and
Fe3+) in MnFe2O4 have synergistic effect on promoting sensor
behavior [97].
The modification of electrode with MnFe2O4 NPs provided
excellent properties like high surface area, high electron transfer
kinetic on surface of the electrode, and high selective electrochem-
ical measurement of the analyte [21]. However, the main barriers
involved in the application of MnFe2O4 NPs in electrochemical sen-
sors are poor electrical conductivity and expansion attributed to
the charging-discharging processes [21,98]. Such problem was
resolved by graphene oxide (GO) as conductive substance which
was incorporated with MnFe2O4 (Table 7). So, the conductivity
and specific surface area of MnFe2O4 NPs/GO composite increased
owing to synergetic effect from the presence of GO and MnFe2O4
NPs [99].
Carbonaceous entities like carbon nanotubes (CNT) was also
used in combination with metal NPs to increase surface area,
improve electron transfer rate, and achieve high electrical conduc-
tivities [100]. In compare to the bare glassy carbon electrode (GCE)
and N-doped CNT, the electrocatalytic activities of ternary compos-
ites (GCE/MnFe2O4/CNT-N) were significantly improved due to
combined beneficial properties of CNT-N (high electrical conduc-
tivity) and sensing properties of MnFe2O4 NPs [101].
Further, Table 7 summarizes the details of MnFe2O4-based mul-
ticomponent composites used as mediator to modify electrode in
the detection of various analytes.
The modified electrode by MnFe2O4 NPs exhibited high selectiv-
ity [34] and sensitivity [34,36,97] as well as long-term stability in
gas sensors [97]. Use of spherical MnFe2O4 NPs in a gas sensor led
to the detection of ammonia at low concentration of 10 ppm at
30°C [34]. The detection of xylene at concentration of 200 ppm
was reported using MnFe2O4 NPs at temperature 25–30°C [104].
Zhang et al. [97] used hollow MnFe2O4 nanoboxes-based metal
oxide semiconductor for the detection of ethanol. Application of
this nanostructure resulted in fast response and recovery time of

Table 6
Comparison of catalytic activities of MnFe2O4-based nanostructures.

Catalyst Target pollutant Degradation Ref.

Composition Action
MnFe2O4 H2O2 activation Norfloxacin 90.6% at neutral pH within 180 min [22]
MnFe2O4/bio-char Tetracycline 95% at pH 5.5 within 120 min [90]
MnFe2O4/Rgo Methylene blue 100% within 130 min [94]
DNSA/CS/MnFe2O4 Methylene blue 98.9% at pH 9 within 30 min [87]
MnFe2O4/MoS2 Acid Blue 113 99% at pH 6.3 within 42 min [91]
Fe0/C/MnFe2O4 TBBPA 90% within 120 min [13]
MnFe2O4/g-C3N4 PMS activation Triclosan 93.2% within 30 min at neutral pH [92]
MnFe2O4/MnO2 Rhodamine B 99% within 5 min at neutral pH [16]
MnFe2O4 -MFC Orange II 100% at pH 7–8 [26]
MnFe2O4/rGO Organic dyes 90% within 120 min [93]
MnFe2O4 Paracetamol 100% [95]
MnFe2O4/b-CD 2,4-DCP 100% within 60 min at neutral pH [88]

Abbreviation: rGO: reduced graphene oxide; DNSA: 3,5-dinitrosalicylic acid; CS: chitosan; C: carbon; g-C3N4: graphitic carbon nitride; MFC: microbial fuel cell; b-CD: b-
cyclodextrin; 2,4-DCP: 2,4-dichlorophenol.

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N. Akhlaghi and G. Najafpour-Darzi
Table 7
Comparison of the sensing characteristics of MnFe2O4 NPs in electrochemical sensors.
Electrode material Sensing compound
CPE/MnFe2O4 Flunitrazepam
CPE/MnFe2O4/MWCNTs Warfarin
GCE/MnFe2O4/CNT-N Caffeine
GCE/MnFe2O4/CNT-N Acetaminophen
GCE/MnFe2O4/CNT-N Ascorbic acid
GCE/rGO/MnFe2O4/Polyaniline Nitrite
GCE/CS/MnFe2O4/Hb H2O2
GCE/MnFe2O4/GO Pb (II)
GE/MnFe2O4 NCs As (III)
Abbreviation: LOD: limit of detection; CPE: carbon paste electrode; MWCNTs: multi-walled carbon nanotubes; GCE: glassy carbon electrode; CNT-N: N-doped carbon
nanotubes; rGO: reduced graphene oxide; CS: chitosan; Hb: hemoglobin; GO: graphene oxide; GE: gold electrode; NCs: nanocrystal clusters.
7.5 and 8 s, respectively. The fast response could be attributed to
the special structure of the mediator which has provided high
active sites for the adsorption and reaction between sensing mate-
rials and oxygen ions. The superior performance of MnFe2O4 NPs is
attributed to their advantageous structure. Porous structure of
MnFe2O4 NPs is efficient in enhanced gas diffusion and adsorption
[34]. In other words, inner and outer surface of NPs increased at
hollow or mesoporous structure, facilitating adsorption of more
oxygen species.
The fundamentals behind the gas sensing principle of MnFe2O4
NPs can be explained based on surface controlled mechanism [97].
When exposing MnFe2O4 NPs to air, adsorbed oxygen species (O 2,
O , O2 ) are generated on the surface of NPs through capturing free
electrons from the conduction band of MnFe2O4 NPs [34]. The
formed oxygen species play important role in the gas sensing pro-
cess. After the electron extraction, the electron-depletion layer
(EDL) is formed on the surface, inducing surface resistance. Upon
the introduction of gas, the gas molecules react with the adsorbed
oxygen ions and can also directly absorb onto the NPs surface. So,
the adsorbed oxygen species get desorbed to the conductive band,
resulted in decrease of resistance [97].
In brief, MnFe2O4 NPs possess good sensitivity in chemical sen-
sors by providing high specific surface area as active sites for the
adsorption and reaction of the target materials. These NPs can be
used as extremely sensitive material for detection of gas molecules
at ambient temperature. Much desired analytical results can be
obtained by improving the conductivity of MnFe2O4 NPs by prepa-
ration of a composite of MnFe2O4 NPs with carbonaceous materials.
Hydrogen production
Hydrogen (H2) is a clean fuel with high energy content
(122 kJ/g); that only water is generated as a by-product of the com-
bustion [105]. Considering the nature of the chemical process,
hydrogen production methods can be divided into three groups:
Thermochemical, biological, and electrochemical methods. Among
these methods, high-temperature thermochemical processes can
generate hydrogen from a clean energy source like water.
In traditional two-step thermochemical cycle, metal oxides can
be used as catalyst for water splitting. In this approach, the metal
oxide (MO) acts as the redox pair MOred/MOox in oxygen releasing
and hydrogen production steps according to the following reac-
tions [106].
1
MOox þ thermal energy ¼ MOred þ O2
2 migration activity [110]. Different methods like ion exchange,
MOred þ H2 O ¼ MOox þ H2
3+
Mn is a strong oxidant and the reduction potential of
Mn3+/Mn2+ pair (+1.51 V) as metal ions is one of the largest redox
potential [106]. Use of thermal energy, the Mn3+ is reduced to
Journal of Industrial and Engineering Chemistry 103 (2021) 292–304
Sensitivity (mA/mM) LOD (mM) Linear range (M) Ref.
6 4
0.752 0.33 0.110 – 1.010 [21]
– 0.08 0.1106 – 4.47104 [102]
0.034 0.83 1.0106 – 1.1103 [101]
0.123 0.83 1.0106 – 1.0103 [101]
0.021 1.8 2106 – 1.0104 [101]
– 0.015 5108 – 1.2102 [99]
– – 1.0106 – 4104 [35]
33.9 0.0883 – [98]
22.1 0.026 – [103]
Mn2+, associated with O2 generation. Then, in the reaction with
water molecules hydrogen is generated by reduced form of MnO
[106].
Although hydrogen production through those reactions is sim-
ple and can be easily manipulated, the reduction temperature for
oxygen generation is usually high (1300°C) [107]. Use of multicom-
ponent compounds like MnFe2O4 NPs, the reaction temperature
could be significantly reduced [107]. Varsano et al. [108] used a
solar reactor-receiver packed with MnFe2O4/Na2CO3 pellets.
Hydrogen was produced in the range of 130–460 mmol/g of mix-
ture at temperature range of 750–800°C for duration of 1 h.
Another work performed by Chen et al. [107] investigated the
influence of size and crystallinity of MnFe2O4 NPs in a composite
system of MnFe2O4/Na2CO3 on hydrogen production at reaction
temperature of 800°C. According to the reported data, use of
MnFe2O4 NPs at small size resulted in high hydrogen productivity;
that is due to high solid–solid contact between MnFe2O4 and Na2-
CO3 materials which provide a homogeneous mixture. In addition,
hydrogen production increased by a moderate increase in the crys-
tallinity of MnFe2O4 NPs which is benefited from the high ionic
transportation.
Inoue et al. [106] reported 60% H2 production yield at 999.85°C
through two-step water splitting processes using H2O/ZnO/MnFe2-
O4 system. Both MnFe2O4 and ZnO have the ability to split water
molecules and produce monophase product. Meanwhile, the Zn/
ZnO system without iron ions has disadvantage of covering the
surface of metallic Zn powder with ZnO layer; which has negative
effect on the reaction between H2O and metallic Zn [106]. In H2O/
ZnO/MnFe2O4 system, hydrogen was produced with incorporation
of Zn2+ cations into MnFe2O4 NPs without transformation of
crystal-structure. In fact, most of the Mn2+ cations were located
in the A-sites of spinel structure. After oxidation of Mn2+ to Mn3+,
the Mn3+ cations moved to the B-site, at the same time Zn2+ incor-
porated into the A-site [106].
Generally, MnFe2O4 NPs can be used as redox pair in multi-step
thermochemical hydrogen production using water as feed. Based
on the above discussion, MnFe2O4 nanoparticle with small size
and fine crystallinity is in favor of high rate of hydrogen production
in thermochemical water splitting.
Heavy metal removal
Heavy metals are defined as metallic elements with high den-
sity (more than 5 g/cm3) [30,109]. They are a serious environmen-
ð3Þ tal issues because of toxicity to living organisms, persistence, and
extraction, reverse osmosis, adsorption, oxidation–reduction,
ð4Þ
chemical and electrochemical precipitation have already been
employed to remove heavy metals from the effluent [30,111].
Among the mentioned methods, adsorption is a suitable approach
that extensively used in the remediation of heavy metals, benefited
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N. Akhlaghi and G. Najafpour-Darzi
from high removal efficiency, convenient operation, low cost, and
generation of low harmful by-products [111,112].
In heavy metals removal, the use of MnFe2O4 NPs as desired
adsorbent combines the advantages of both nanotechnology and
magnetic separation. In fact, MnFe2O4 is responsible for developing
charge on the surface of MnFe2O4-based adsorbents when it inter-
acts with water [113]. Based on literature, MnFe2O4 NPs demon-
strated adsorption capacities of 34.84 mg/g (at pH 2) and
39.6 mg/g (at pH 5) for the removal of Cr (VI) and Cr (III) ions,
respectively [29].
Nevertheless, MnFe2O4 NPs strongly tend to aggregate in aque-
ous phase that could reduce its surface area resulting in low
adsorption capacity. To overcome this problem, coating of NPs
with organic or inorganic layers was carried out. In this context,
we can emphasize core–shell structures, in which the shell can
preserve the magnetite core and also provide NPs with feasible
surface appropriate for further functionalization with organic or
inorganic compounds. Reddy et al. [31] reported adsorption capac-
ity of 380 mg/g for removal of Pt (IV) in hydrochloric acid solution
using amino-functionalized MnFe2O4-silica-core shell NPs. Under
such acidic condition, the Pt (IV) in the form of anionic chloro-
2
complexes (PtCl6 ) adsorbed on the sorbents through electrostatic
attraction between protonated amine groups of MnFe2O4/SiO2-NH2
NPs and anionic Pt-Cl complexes (Fig. 5(i)). In other words, silica
coating of the magnetic MnFe2O4 NPs not only prevented NPs
aggregation but also improved the chemical stability of NPs at
low pH values [31].
Coating of MnFe2O4 NPs with cellulose for the removal of Cr (VI)
was reported by Ghanbarian et al. [114]. They compared adsorp-
tion capacity of magnetic nanocellulose (MC) with amino-
functionalized MnFe2O4-cellulose (AFMC) NPs and cellulose.
Owing to higher active surface area and existence of amino groups
on the AFMC NPs, the adsorption capacity of AFMC (250 mg/g) was
much higher than MC (125 mg/g) and cellulose (25 mg/g) under
the same condition (acidic pH). As shown in Fig. 5 (ii), Cr (VI) can
be removed through electrostatic attraction and complexation
between amine and hydroxyl groups of AFMC NPs and anionic spe-
cies of Cr (VI) like HCr2 O 2
7 and CrO4 .
Fig. 5. (i) adsorption of Pt (IV) on ((3-aminopropyl) triethoxysilane (APTES))-functionalized silica-coated MnFe2O4 NPs at acidic pH [31], (ii) adsorption of Cr (VI) on amine
modified MnFe2O4-cellulose NPs [114]
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Journal of Industrial and Engineering Chemistry 103 (2021) 292–304
In this context, adsorption capacity of MnFe2O4 NPs enhanced
by employing combination of MnFe2O4 NPs with chitosan as a bio-
compatible polymer. Use of MnFe2O4/chitosan NPs, adsorption
capacities of 60.6 mg/g and 62.3 mg/g were reported for the
removal of Cd (II) and Cu (II) ions at pH 6, respectively [111]. In
addition to chitosan, graphene oxide (GO) as carbonaceous mate-
rial was widely used for heavy metal removal due to high effective
surface oxygenous functional groups as adsorption sites [115]. The
results of heavy metal adsorption capacity using MnFe2O4 NPs/GO
were 366.4 mg/g (at pH 5.5), 97 mg/g (at pH 6.5), 488 mg/g (at pH
5), and 136 mg/g (at pH 4) for the removal of Pb (II) [112], As (III),
Pb (II), and As (V) [116], respectively.
From the above discussion it can be concluded that higher
adsorption capacity for heavy metal ions can be obtained using
combination of MnFe2O4 NPs with GO in compare to MnFe2O4/chi-
tosan NPs and bare MnFe2O4 NPs, as well, due most likely to dis-
tinctive functional groups of GO and providing high surface area
through coupling with GO for metal ions adsorption.
Other composite structures of MnFe2O4 NPs were fabricated
with successful performance in heavy metal removal. Jin et al.
[117] evaluated the adsorption performance of L-cysteine immobi-
lized hollow MnFe2O4 nanosphere for the removal of Pb (II). The
literature results demonstrated an adsorption capacity of
268.86 mg/g at pH 7 for the synthesized nanostructure. Wadhawan
et al. [118] comprehensively reviewed the effect of temperature,
contact time, adsorbent dose, pH, and ionic strength on adsorption
of heavy metal on NPs. So, we will not further review these param-
eters herein.
The adsorption of heavy metal ions on MnFe2O4-based adsor-
bents includes various mechanisms. Podder et al. [113] reported
adsorption of As (III) and As(V) on Sawdust/MnFe2O4 composite
through electrostatic interaction between the –OH groups of bio-
sorbent and metal ions. Liu et al. [119] revealed the role of –OH
and –NHþ 3 functional groups located on MnFe2O4/chitosan/SiO2
microsphere in the adsorption of Zn2+ ions through chelation and
complexation reaction. Hu et al. [120] demonstrated the combina-
tion of ion exchange and electrostatic interaction in adsorption of
Cr (VI) on the modified surface of MnFe2O4 NPs. Dai et al. [112]
N. Akhlaghi and G. Najafpour-Darzi
reported adsorption of Pb (II) on hybrid MnFe2O4/GO composite
through cation exchange between positively charged heavy metal
ions and GO-COO and GO-O located on the surface of the
adsorbent.
Generally, MnFe2O4 NPs can be used as adsorbent for the
removal of heavy metal ions at various pH values, depending on
the functional groups located on NPs surface and mechanism of
adsorption process. Owing to large surface area of GO along with
distinctive functional groups, combination of GO with MnFe2O4
NPs enhanced adsorption capacity of the adsorbent.
Drug delivery
MnFe2O4 NPs have been found application in nanotechnology-
based transport vehicles owing to high hydrophilic and magnetic
properties. Meanwhile, appropriate surface functionalization is
necessary for having high drug loading capacity with intelligent
controlled release. Naderi et al. [121] reported 67.2% curcumin
loading on MnFe2O4 NPs/carboxymethyl chitosan hydrogel
through hydrogen-bonding interaction between NH2 groups of
the chitosan and hydroxyl groups of the drug (Fig. 6(i)).
Akhlaghi et al. [28] investigated covalent immobilization of
ampicillin on NH2-functionalized MnFe2O4/SiO2 core–shell NPs
(Fig. 6 (ii)). Modification of silica shell on MnFe2O4 NPs not only
prevents NPs to form agglomeration but also provides lots of
hydroxyl groups on the surface which are suitable for further func-
Fig. 6. (i) curcumin immobilization on MnFe2O4/carboxymethyl chitosan hydrogel
prepared by using epichlorohydrin as cross-linker [121], (ii) ampicillin immobi-
lization on MnFe2O4/SiO2-NH2 NPs [28]
301
Journal of Industrial and Engineering Chemistry 103 (2021) 292–304
tionalization of NPs with desired molecules like APTES through
condensation [23]. Use of this nanostructure, 50% reduction in
minimum inhibitory concentration (MIC) of ampicillin against
Escherichia coli bacteria was reported.
Fahmi et al. [122] evaluated immobilization of naproxen on
MnFe2O4 NPs/cellulose acetate nanofibers prepared via electro-
spinning. Based on reported results, the release rate of naproxen
in neutral pH was higher than that in basic and acidic conditions
due to low electrostatic attraction in neutral pH value. Wang
et al. [123] reported doxorubicin loading capacity of 0.97 mg/mg
for MnFe2O4/graphene oxide nanocomposite. The loaded doxoru-
bicin demonstrated pH-dependent release manner. According to
the reported data, within 24 h, the release rate of doxorubicin
under pH 4 (70%) was much higher than that at neutral pH 7.4
(22%) and alkaline pH value of 9 (31%), which is suitable for treat-
ing cancerous tissues at acidic microenvironments. This phe-
nomenon could be attributed to the stronger hydrogen-bonding
interaction between hydroxyl and carboxylic groups of graphene
oxide and drug functional groups (OH and NH2) under neutral
and alkaline conditions in compare to acidic conditions.
In short, MnFe2O4 NPs as magnetic carrier have been used for
the immobilization of various therapeutics through entrapment,
covalent and hydrogen-bonding interactions. The loaded drugs
demonstrated pH-dependent release manner depending on the
strength interactions at different pH values between the functional
groups of drug and effective functional groups on the surface of
NPs.
Concluding remarks
MnFe2O4 NPs have aroused growing interest in the past decade
in view of their soft magnetic behavior, high saturation magnetiza-
tion, and biocompatibility. From this review, it can be concluded
that synthesis method, operation conditions, and concentration
of precursors were effective factors on the size, morphology, pur-
ity, and crystallinity of MnFe2O4 NPs. Properties like heat genera-
tion, saturation magnetization, surface area, specific absorption
rate, transverse relaxivity, reversible capacity, and specific capaci-
tance are influenced by the preparation method, size, shape, and
functional groups coated on MnFe2O4 NPs. Depending on the need
of application, suitable synthesizing method under optimum con-
ditions should be selected to provide NPs with desired properties.
Various synthesizing methods were used in each nine applications
of MnFe2O4 NPs as discussed in the above sections. In other words,
no application was restricted to a single synthesis method. Based
on our survey, hydrothermal is the most reported synthesis meth-
ods used in supercapacitors, LIBs, and catalyst applications. The co-
precipitation approach was mainly employed in the synthesis of
MnFe2O4 NPs for heavy metal removal, hyperthermia therapy,
and drug delivery applications. Thermal decomposition and
solvothermal methods were the common used methods in the
other applications.
Overview on applications of MnFe2O4 NPs demonstrated the
efficiency of these NPs in catalyzing the degradation of dyes and
drugs at neutral pH, which is in favor of the industrial application.
MnFe2O4 NPs with fine crystallinity and small size is preferred for
high rate hydrogen production through thermochemical water-
splitting reaction. The performance of MnFe2O4 NPs as an adsor-
bent in the removal of heavy metal was notable at a wide range
of pH values. Besides, MnFe2O4 NPs can be considered as a promis-
ing carrier for immobilization of various therapeutics including
antibacterial, anti-cancer, and anti-inflammatory drugs.
To meet the requirement of local heat generation and high
relaxivity values in magnetic hyperthermia therapy and magnetic
resonance imaging (MRI), respectively, MnFe2O4 NPs with high sat-
N. Akhlaghi and G. Najafpour-Darzi Journal of Industrial and Engineering Chemistry 103 (2021) 292–304

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