Journal of Magnetism and Magnetic Materials 368 (2014) 207–229

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Journal of Magnetism and Magnetic Materials

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

Review

Progress in electrochemical synthesis of magnetic iron

oxide nanoparticles
Donya Ramimoghadam, Samira Bagheri n, Sharifah Bee Abd Hamid
Nanotechnology & Catalysis Research Centre (NANOCAT), IPS Building, University of Malaya, 50603 Kuala Lumpur, Malaysia

art ic l e i nf o a b s t r a c t

Article history: Recently, magnetic iron oxide particles have been emerged as significant nanomaterials due to its
Received 17 February 2014 extensive range of application in various fields. In this regard, synthesis of iron oxide nanoparticles with
Received in revised form desirable properties and high potential applications are greatly demanded. Therefore, investigation on
8 April 2014
different iron oxide phases and their magnetic properties along with various commonly used synthetic
Available online 29 May 2014
techniques are remarked and thoroughly described in this review. Electrochemical synthesis as a
Keywords: newfound method with unique advantages is elaborated, followed by design approaches and key
Iron-oxide nanoparticles parameters to control the properties of the iron oxide nanoparticles. Additionally, since the dispersion of
Electrooxidation iron oxide nanoparticles is as important as its preparation, surface modification issue has been a serious
Superparamagnetic iron-oxide
challenge which is comprehensively discussed using different surfactants. Despite the advantages of the
Surface modification
electrochemical synthesis method, this technique has been poorly studied and requires deep investiga-
tions on effectual parameters such as current density, pH, electrolyte concentration etc.
& 2014 Elsevier B.V. All rights reserved.

1. Introduction
1.1. Iron oxide phases and its properties
Iron oxides are classified as the substantial transition metal
oxides taking advantage of technological importance. In nature,
iron oxides can be found in many different forms [1]. Sixteen pure
phases of iron oxides, particularly, oxides such as Magne-
tite, Hematite, Iron oxide beta phase and Maghemite, hydroxides
such as Iron(III) hydroxide or Bernalite, Iron(II) hydroxide, oxy-
hydroxides such as Geothite, Akaganetite, Lepidocrocite, Feroxy-
hyte are known to date. Trivalent state, distinct colors and low
solubility are characteristics of these compounds [2]. Among entire
iron oxides and hydroxides, only Schwertmannite (iron-oxyhy-
droxysulfate) and ferrihydrite (hydrous ferric oxyhydroxide) are
poorly crystalline.
One of the most important iron oxide, black in color and
ferromagnetic, is Magnetite (Fe3O4) which contains both Fe(II) and
Fe(III). Although stoichiometric magnetite has Fe(II)/Fe(III) equals to
0.5 but magnetite, which is frequently non-stoichiometric results in
a Fe3 þ deficient layer. Magnetite has an inverse spinel crystal
structure with a face-centered cubic unit cell having an edge length
of 0.839 nm and 32 oxygen atoms. In this particular crystal
structure Fe2 þ and half of the Fe3 þ occupy octahedral sites and
n
Corresponding author.
E-mail address: samira_bagheri@um.edu.my (S. Bagheri).
the other half of the Fe3 þ occupies tetrahedral sites. Divalent iron
atoms prefer to take octahedral sites to obtain higher crystal field
stabilization energy. However, the trivalent iron atoms occupy the
two octahedral and tetrahedral sites (crystal field stabilization
energy¼ 0). The actual crystal types of magnetite consist of octahe-
dron and rhombodecahedron with surface area in the range of
4 to100 m2 g  1 [3].
The second important and common iron oxide is hematite
(α-Fe2O3). Hematite is iso-structural with corundum (α-Al2O3),
consisting of a dense arrangement associated with Fe3 þ ions in
octahedral coordination with oxygens in hexagonal closest-
packing. The crystal system of hematite is hexagonal with the
lattice parameters of a ¼5.0346 Å, c¼ 13.752 Å, however crystals
include lots of forms. The structure can be also ascribed as the
stacking of Fe3 þ ions sheets between two closed-packed layers of
oxygens, holding together by covalent bond. The structure in
addition has a three-dimensional framework developed along
with trigonally distorted octahedra FeO6, linked to thirteen neigh-
bors by one face, three edges and six vertices. Because Fe is in a
trivalent state (ferric Fe), each one of the oxygens is actually
bonded with just two Fe ions, and so, only two out of three
available oxygen octahedrons are occupied. This specific arrange-
ment tends to make the structure neutral with no deficit or charge
excess. Hematite's specific surface area ranges from 10 to
90 m2 g  1 [3].
Goethite, common form of iron oxy-hydroxide, α-FeO(OH) exhi-
bits an orthorhombic crystal structure with lattice parameters of
a¼9.95 Å, b¼3.01 Å, c¼4.62 Å. This structure is a three-dimensional

http://dx.doi.org/10.1016/j.jmmm.2014.05.015
0304-8853/& 2014 Elsevier B.V. All rights reserved.
208 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
structure built up with FeO3(OH)3 octahedra forming large tunnels,
spreading out along the direction (0 1 0) whereas hydrogen atoms
are positioned. Each octahedron is linked to eight neighboring
octahedral by four edges and three vertices. Oxygen atoms are in
tetrahedral surroundings, either OFe3H or OFe3H (bond). Goethite
can be found in different shapes and morphologies; however, its
morphology mostly is acicular. Its specific surface has been reported
from 8 to 200 m2 g  1 [3].
Ferrihydrite is generally accustomed to explain both 2- or 6-line
ferrihydrite, which have either two or six identifiable broad reflections
in a diffraction pattern. Ferrihydrite has different chemical formulae,
including Fe5HO8  4H2O, Fe5(O4H3)3, Fe2O3  2FeOOH  2.6H2O and
5Fe2O3  9H2O [4]. The shape of ferrihydrite is spherical and unlike
other iron oxide phases it forms only as nano crystals representing
high specific surface areas in the range of 100 to 700 m2 g  1 [3]. The
structure of ferrihydrite continues to be controversial as the lowest
degree of order hinders the clarification of the structure.
Wüstite (FeO) is another phase of iron oxide with a cubic unit
cell. This phase is stable under thermal equilibrium at high
temperatures (above 843 K) and low pressures. The large O2 
anions form a close packed fcc sublattice with the small Fe2 þ
cations which occupied the interstitial sites. Just about all Fe ions
are octahedrally coordinated to oxygen [5]. In Wüstite, the oxygen
and iron (1 1 1) planes form ideal two-dimensional hexagonal
lattices with an inter-atomic distance of 3.04 A, which usually
corresponds to the lattice constant of the hexagonal unit cell on
the unreconstructed FeO(1 1 1) surface. Along the (1 1 1) direction
the iron and oxygen (1 1 1) planes form the cubic ABC stacking
sequence with an interlayer distance of 1.25 A. The length of the
iron–oxygen bond is 2.16 A.
Akaganeite (β-FeOOH) is an iron oxyhydroxide phase with
largest tunnel-type structure among all other phases. In this
structure, iron atoms are powerfully bonded to the framework.
In akaganeite the octahedral sites are generally occupied by
FeH and Cl and perhaps H2O is presumably located in the tunnels
(Cl  is considered as an impurity) [6].
Lepidocrocite (γ-FeO(OH)) with crystal structure of Orthor-
hombic, is assembled by double layers of Fe-octahedra, and
hydroxyl groups which occupied their external surfaces and
allowing the formation of hydrogen bonding between the layers.
It is believed that hydrogen atoms are located at the centers of
inversion and occupied the same distances from two oxygen
atoms of the adjacent layers, therefore producing continuous
O–H–O–H–O chains with hydrogen bonds symmetry. The main
morphology of lepidocrocite is either lath-like or tabular and the
surface area are usually between 15 and 260 m2 g  1 [3]. Table. 1
summarizes all information regarding to iron oxide different
phases and properties.
1.2. Applications of iron oxide nanoparticles
Iron oxide nanoparticles are widely used as highly active
catalysts which have been applied in several oxidation/reduction
and acid/base reactions [7]. Iron oxide-based materials are
counted to be cheap and efficient candidates in environmental
catalysis. Recent synthetic advances have resulted in iron oxide
nano-particles are considerably more effective than conventional
larger-sized iron oxide [8,9] for the oxidation of carbon monoxide
and the oxidative pyrolysis of biomass [9] or biomass model
compounds [10,11]. The reason can be explained based on the
fact that nanoparticles have the enhanced surface area ratio and
more coordination of unsaturated sites on their surfaces which
leads to their higher activity. Moreover, matrix supported nano-
particles, which have indicated improved stability have found a
broad application as catalysts. Magnetite and hematite are the
most common catalysts were employed among all types of iron
oxides. In addition, catalytic activity of heterogeneous catalyst
with iron oxide and heterogeneous catalyst based on magnetic
mixed iron oxides has been widely investigated [12]. For instance,
LixCul  yFeyO [13,14] nanoparticles have been assessed as potential
components of lithium-ion batteries.
Magnetic nanoparticles were also explored for their potential
application as high-density magnetic data storage. If a single nano-
particles with size of 5 nm can storage individual bit of information,
so storage density of 10 Gbit cm  2 would not be impossible [15].
Magneto-optical switches are another application of iron oxide
nanoparticles. They have also revealed which are applicable in
sensors based on giant Magnetoresistance [16–18], magnetically
controllable Single Electron Transistor devices [19–21] and photonic
crystals [22].
Dilute magnetic semiconductors (DMS), which have recently
attracted lots of attention, is doped iron ions into the semicon-
ductors to optimize the optical and electronic properties of
magnetic nanoparticles and semiconductors [23]. DMS nanoparti-
cles can be applied in the production of novel optical materials.
Additionally, DMS nanoparticles show strong photoluminescent
emission of green light [18]. Moreover, the electronic character-
istics of DMS nanoparticles sense both light and magnetic fields
that represent their functionality in the magneto-optical switches’
fabrication [24,25].
Magnetic iron oxide nanoparticles have also displayed a large
number of biomedical applications; the most common application
is considered in Magnetic Resonance Imaging (MRI) as contrast
agents [26–29]. Researchers were able to develop bio-conjugated
magnetic iron oxides which involved targeting of MRI probes
towards the brain tumors along with its real-time monitoring [30].
Drug delivery or Magnetic drug targeting has been recently
focused on application of iron oxide nanoparticles as carriers,
which preventing the conventional chemotherapy side effects and
representing a promising cancer cure.
Iron oxide nanoparticles are also able to nucleate and control
the high aspect ratio nanomaterials growth like carbon nanotubes
(CNTs), where a substrate is coated with iron nanoparticles and
CNTs are thereby grown applying various chemical vapor deposi-
tion processes. Nanoparticles of irons and its compounds [31–33]
have shown their reactivity in the mentioned processes. In the
case of iron nanoparticles, the diameter of CNT can be controlled in
the range of 3–13 nm by the diameter of the nucleating iron
nanoparticles [34].
Iron oxide nanoparticles can be utilized to remove toxic waste.
Bulk iron oxide can act as reducing agent and decompose various
toxic chemicals and compounds in aqueous solutions [35,36].
As mentioned before, due to large surface area, nanoparticles are
more efficient at wastewater treatments, for instance iron nano-
particles could remove Cr4 þ and Pb2 þ from aqueous solutions
[37].
A Large amount of synthetic (63%) and natural (37%) iron
oxides is used as pigment world-widely. The commonly used iron
oxides such as goethite, magnetite, maghemite and hematite
are applied as pigments to produce yellow, black, brown and
red colors, respectively. Reduction in the particle size and achiev-
ing nano-sized particles assist to obtain transparent iron oxide
pigments.
Several studies have been concentrated on γ-Fe2O3 (Maghemite)
and β-Fe2O3 phases, indicates suitable sensing characteristics
towards carbon monoxide, hydrocarbon gases and alcohol [38–44]
and therefore can be employed in gas sensing applications.
Iron oxides have extensive applications as pigments, catalysts,
coatings, lubrication, ion exchangers, sorbents, and gas sensors
[45–50]. Moreover, Iron oxide nanoparticles and nanocomposites
have potential applications in different areas like magnetic data
storage devices, magnetic recording, inks and toners for xerography,
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229 209

Table 1
Characteristics and properties of iron oxide phases [2,3].

Iron oxide phases Chemical Oxidation state Crystal structure Magnetism Color
formula

Magnetite Fe3O4 þ 2, þ 3 (average Cubic a¼ b¼ c Ferrimagnetic Black/brownish

2.67) black
Hematite α-Fe2O3 þ3 Rhombohedral a ¼b ¼ c α a βa γ Weakly ferromagnetic/ Red
antiferromag
Iron oxide beta phase β-Fe2O3 þ3 Cubic a¼ b¼ c Paramagnetic –
Maghemite γ-Fe2O3 þ3 Cubic a¼ b¼ c or tetragonal Ferrimagnetic Reddish-brown
Goethite α-FeO(OH) Orthorhombic a ab a c α ¼ β¼ γ ¼901 Antiferromagnetic Yellowish brown
Akaganeite β-FeO(OH) Monoclinic a ab a c α ¼ β¼ 901 Antiferromagnetic Yellowish brown
γ ¼ 1201
Lepidocrocite γ-FeO(OH) Orthorhombic a ab a c α ¼ β¼ γ ¼901 Antiferromagnetic Orange
Feroxyhyte δ-FeOOH Hexagonal a ¼b a c α¼ β ¼901 Ferrimagnetic Red-brown
γ ¼ 1201
Iron(III) hydroxide Fe(OH)3 Orthorhombic a ab a c α ¼ β¼ γ ¼901 – Dark green
(Bernalite)
Iron(II) hydroxide Fe(OH)2 – – Green
Ferrihydrite Fe5HO8  4H2O Hexagonal a ¼b a c α¼ β ¼901 Speromagnetic Red-brown
γ ¼ 1201
Wüstite FeO þ2 Cubic a¼ b¼ c Antiferromagnetic Black

Magnetite Catalyst

Hematite Magnetic data storage

Maghemite Semiconductors

Geothite MRI

Akaganeite Waste-water treatment

Iron oxide
Lepidocrocite Pigment
Nanoparticles
Feroxyhyte Gas sensing

Iron hydroxide Coatings

Ferrihydrite Lubrications

Wüstite Sorbents

Fig. 1. Various phases and applications of iron oxide nanoparticles.

and wastewater treatment, magnetic resonance imaging, bio- is expressed by Eq. (II),
separation, and medicine [51–57]. Iron oxide nanoparticles can be
B ¼ μðH þ JÞ ðIIÞ
used as transparent iron oxide pigments since they have durability
and UV absorbing properties [58]. Fig. 1 shows extensive applica- Magnetic permeability, μ, can be defined as the tendency of the
tions of iron oxide nanoparticles along with its different phases. magnetic lines of force to go through a medium relative to their
tendency to pass through a vacuum. This is the parameter that
discriminates between diamagnetic and paramagnetic materials.
2. Magnetic properties of iron oxide phases Permeability is calculated by,

2.1. Magnetic properties

μ ¼ μ0 ð1 þ kÞ ðIIIÞ

where μ0 is the magnetic permeability in the vacuum.

Magnetic properties of solids are characterized by considering Another parameter to quantify the magnetic properties of a
important parameters such as magnetic susceptibility, the perme- material is magnetic moment, m. Although it is not measured
ability and the magnetic moment. When a substance is located in a directly, but can be calculated from the measured molar suscept-
magnetic field of strength, H (units Tesla), the magnetization ibility to which it is related,
intensity, J, which is related to H by the magnetic susceptibility,
ĸ, of the substance [59], N m2
χ ¼ μ0 ðIVÞ
3kT
J ¼ ĸH ðIÞ
where N is the Avogadro number and k is the Boltzmann constant
Magnetic susceptibility can be indicated in terms of volume, as [60]. The fundamental magnetic moment is the Bohr magneton, β,
ĸ (m3 m  3 or J T  2 m  3), or mass, χ (m3 kg  1 or J T  2 kg  1). The
density (or flux) of the lines of force in a solid located in a eh
β¼ ¼ 9:2734 U 10  24 Am2 ðVÞ
magnetic field (H) is introduced as the magnetic induction, B, and 4 π me c
210 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
where me and e are the mass of the electron and charge, respec-
tively. Eq. (IV) can be minimized to:
pffiffiffiffiffiffi
m ¼ 2:83 χ T ðVIÞ
The magnetic moment’s unit is Joule/Tesla, but often shown in
Bohr magnetons. The magnetic moment emerges due to the
interaction between the spin moment of the electron, μs and the
orbital moment; the contribution of the orbital moment is of
relatively minor importance [59]. The magnitude of the overall
spin moment depends on the number of unpaired electrons in the
atom, i.e.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
μs ¼ g SðS þ1Þ ðVIIÞ
S is the sum of the spin quantum numbers, to which each electron
contributes þ 1/2; and g is the gyromagnetic ratio (i.e. the ratio of
the magnetic moment of the angular momentum), for a free
electron, g ¼2.
High spin Fe3 þ owning five unpaired d electrons shows both
the calculated and measured magnetic moments are 5.9 Bohr
magnetons (BM) due to the zero orbital angular momentum, while
the measured magnetic moment for Fe2 þ is 5.l to 5.5 BM which is
higher than the calculated one indicating a contribution from the
orbital moment of the ion.
2.2. Types of magnetism
Diamagnetism is an intrinsic property of all substances causing
an insignificant repulsion by a magnetic field. Therefore magnetic
susceptibility of a diamagnetic substance is supposed to be small
(  10  6), negative and temperature-independent. Iron oxides
exhibit extra types of magnetism.
Paramagnetic substances are captivated in the direction of a
magnetic field. Such substances contain unpaired electrons which
are randomly aligned on different atoms. Each atom (ion or molecule)
of a paramagnetic substance can be envisaged as a small magnet with
its particular, innate magnetic moment. Using a magnetic field leads
to (partial) orientation of these magnets parallel to the field [61].
The magnetic susceptibility for paramagnetic materials is positive and
small (o0.01). It is temperature-dependent and its behavior can be
expressed by the Curie–Weiss law,
CM
χM ¼ ðVIIIÞ
T TC
where T, CM and TC are the temperature, Curie constant and the Curie
temperature, respectively. The temperature dependence of χM is the
result of two opposing tendencies; as the temperature increases, the
raised alignment of the magnetic moment in the substance is resisted
by the stronger thermal vibrations and leads to χM value reduction.
Below a certain temperature (Neel or Curie) depending on the type of
oxide, compounds undergo a transition to a magnetically ordered state
and became ferromagnetic, ferrimagnetic, antiferromagnetic and/or
speromagnetic. For ferromagnetic and ferrimagnetic materials, the
transition temperature is named the Curie temperature (TC) and for
antiferromagnetic materials the Neel temperature (TN).
Ferro- and ferrimagnetic materials are severely attracted towards
the magnetic field. They contain unpaired electrons whose moments
are due to the interactions between neighboring spins, at least partly
aligned even when no magnetic field presents. Energy of spin coupling
is positive. In a ferromagnetic substance, electron spins possess parallel
alignment. Such substances have an overall net magnetic moment, a
large positive susceptibility (0.01–l06) and a large magnetic perme-
ability. When the temperature rises, the ordered alignment of the
spins reduced in respect to thermal fluctuations of the individual
magnetic moments and the susceptibility drops sharply. The
temperature-dependent behavior of the susceptibility does not obey
the Curie–Weiss law. In an anti-ferromagnetic material, the electron
spins have an equal magnetic moment and are ordered in an anti-
parallel position. Such materials show zero overall magnetic moment,
a small positive susceptibility (0–0.1) and positive permeability.
Temperature increasing usually leads to enhance the susceptibility
since the anti-parallel ordering is distorted. Ferrimagnetic materials
like anti-ferromagnetic ones consist of at least two interpenetrating
sublattices with anti-parallel alignment of spins. In a ferrimagnetic
material, however, different spins have unequal moments; therefore a
ferrimagnetic substance has a net magnetic moment.
Ferromagnetic, ferrimagnetic and anti-ferromagnetic materials
have a domain structure; only the particles with the size of 50 to
500 nm consist of a single domain. The spin within a domain are
either anti-parallel or parallel, but different domains own different
spin alignment. To remove the domains in a ferro- or anti-
ferromagnetic material, an adequately high magnetic field must
be utilized; as the used magnetic field is enhanced, the spins’
alignment will be increased in the domains. At a high sufficient
magnetic field, saturation magnetization is obtained, i.e. all the
domain spins orientation become parallel.
A plot of magnetization versus magnetic field shows a hyster-
esis loop which includes two branches corresponding to the
magnetization and demagnetization processes. The magnitude of
the reverse field needed to demagnetize a ferro- or ferrimagnetic
material is defined as coercivity. Magnets with low coercivity are
expressed “soft”. The term “Hard” refers to magnets having both a
high permanent magnetization and a high coercivity. Therefore
hard materials are not easily demagnetized. Materials applied in
magnetic retarding devices possess coercivities in the range of
5.02 to 18.65 Am  1.
Super-paramagnetism can be arisen due to the magnetic
anisotropy, i.e. when aligned electron spins accompany with
preferred crystallographic directions, it results in easily magneti-
zation of the material. The preferred direction should be along
either one or set of crystallographic axes, for instance [111]
direction is for magnetite. In the case of sufficient energy,
magnetism is usually reversed along these axes. The intransitive
time for spin reversal is termed as the relaxation time; τ which
depends on the energy limit height between the forward and
reverse spin states and the temperature, according to
K eff V
τp ðIXÞ
kT
The height of the energy barrier between the forward and
reverse states is the product of the particle volume, V, and the
anisotropy constant Keff [62]. Superparamagnetic relaxation hap-
pens when the particles’ thermal energy transcends the activation
energy barrier between the spin states and so permits fast,
spontaneous fluctuations between these states. The effect of the
spins reversal results in decrease or even absence of the observed
magnetic field.
Since the existence of the superparamagnetic effect depends on
the size of particles and on the anisotropy constant, it is normally
shown at ambient by o10 nm iron oxides. Superparamagnetic
relaxation may be neutralized by reducing the temperature and
thereby enhancing τ. Superparamagnetic particles usually is
ordered below a blocking temperature TB:
K eff  V
TB ¼ ðXÞ
25k
Speromagnetism is a characteristic of some amorphous or
poorly ordered materials which own metal-O-metal bonds. Metal
may support super-exchange reaction if it carries a magnetic
moment [63]. Fig. 2 shows typical categories of magnetic proper-
ties of materials.
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229 211

Type of
Magnetism

Net No Net
Magnetization Magnetization

Anti-
Ferromagnetism Ferrimagnetism Paramagnetism Diamagnetism
ferromagnetism

Fig. 2. Different types of magnetism (arrows represent the spin orientation).

Table 2
Magnetic properties of the iron oxides (TN, TC and TM are Néel, Curie and Morin transition temperatures, respectively) [66–70].

Iron oxide Magnetic Structure Temperature Anisotropy constant Keff Saturation magnetization at 300 K Magnetic
phases (K) (J m  3) (Am2 kg  1) hyperfine
field (Bhf)

295 K 4 K

Geothite Antiferromagnetic 400 TN 103 0.001–1 38.2 50.6

Lepidocrocite Antiferromagnetic 77 TN – – – 4648.2
Akaganetite Antiferromagnetic 290 TN – – –
δ-FeOOH Ferrimagnetic 440–460 TN – 7-20
Feroxyhyte Ferrimagnetic 455 TC – 59
HP-FeOOH Antiferromagnetic 470 TN
5
Ferrihydrite Speromagnetic E350 TN 10 – 47–50
Bernalite Weakly ferromagnetic E427TN – – 43.1 E 56
Hematite Weakly ferromagnetic/ 956 TC 1–6  104 0.3 51.8 54.2
antiferromagnetic 260 TM
Magnetite Ferrimagnetic 850 TC 104–105 92–100
Maghemite Ferrimagnetic 820–986 TC 105 60–80 50 52.6
ε-Fe2O3 Anti-ferromagnetic 1026 TN – –
Fe(OH)2 Planar antiferromagnetic 34 TN – –
Wüstite Antiferromagnetic 203–211 TN

2.3. Magnetic behavior of iron oxides
The electrostatic exchange interaction is the most important kind
of magnetic interaction among Fe ions on adjoining sites in a solid
material; this leads to make the spins in parallel or anti-parallel
alignment. The Fe3 þ ions in iron oxides are encompassed by O2 or
OH  ions, so the exchange interactions launch via the intervening
ligand. This procedure is called super-exchange. Unpaired electrons in
the eg orbitals of the Fe3þ ions interact magnetically with electrons on
the p orbitals of the O2 ions and, provided the cation and ligand
getting close enough to easily allow coupling of their electrons,
thereby a chain coupling effect which percolates through the crystal,
occurs. The measured exchange constants for these processes found to
be dependent on the bond length and angle. When the Fe3 þ bond
angles are in the range of 120–1801, exchange interactions are strong
while they get much weaker when the angle is 901. Similar depen-
dence on bond angle can be observed for super-exchange interactions
in Fe2þ oxides. Therefore, in the case of magnetite due to the presence
of both Fe2 þ and Fe3þ , electron delocalization can be taken place
between iron ions on an adjacent site.
Mössbauer spectroscopy, neutron powder diffraction and mag-
netometry can be applied to determine the magnetic properties of
iron oxides. A vibrating sample magnetometer (VSM) or Super-
conducting Quantum Interference Device (SQUID) magnetometer
can be employed to examine the magnetic properties of materials.
The magnetic moment, permeability, hysteresis loops, saturation
magnetization, magnetic anisotropy constants and magnetic
hyperfine field (Bhf) are the characteristic parameters [64].
The magnetic hyperfine field Bhf in iron oxides originally comes
from 3d electrons of an atom that polarize the atom’s inner s
electrons. Minor contributions also rooted from the polarization of
the s electrons by the surrounding cations’ 3d electrons and from
the spin dipolar moment of the 3d electrons themselves. Iron oxides
are magnetized spontaneously below TN or TC. As the temperature is
lowered to below for ordering temperature, the Bhf increases and
reaches to the saturation value when temperature becomes. The
presence of a diamagnetic cation like aluminum may lead to
decrease in Bhf value, which can be interpreted according to super
transfer mechanism. In fact, aluminum existence can increase the
Al–O–Fe bond which result in reduction of 3d-spin density super
transfer into the outer s orbital of the iron atom and thereby causes
a hyperfine field to decrease [65] (Table 2).
3. Different synthetic methods of iron oxide nanoparticles
The synthesis of magnetic iron oxide nanoparticles is a com-
plicated process due to their inherent colloidal behavior. The key
212 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
challenge is mostly to optimize the reaction conditions resulting in
a monodisperse solution of magnetic particles with nano-sized
range. The second obstacle is the reproducibility of the synthesis
which enables the process to scale up to industrial scale with no
further purification procedure, such as size-exclusion chromato-
graphy [71], magnetic filtration [72], ultracentrifugation [73], or
flow field gradient [74]. Countless chemical techniques can be
used to synthesize iron oxide nanoparticles, including coprecipita-
tion, hydrothermal reactions [75], sol–gel method [76], microe-
mulsions techniques [77], flow injection synthesis [78], Aerosol/
vapor methods, sonochemical reactions [79], and electrospray
synthesis [80]. All the methods have been utilized to synthesize
particles with small size distribution and homogeneous composi-
tion. Nevertheless, the commonest method for the generation of
magnetite nanoparticles is the chemical coprecipitation technique
of iron salts [81–86].
3.1. Coprecipitation method
The coprecipitation method is the most straightforward and
efficient wet chemical route to synthesize magnetic nanoparticles.
Iron oxides (FeOOH, Fe3O4 or γ-Fe2O3) are normally precipitated
from aqueous solution of Fe(II) and/or Fe(III) salts with alkali along
with suitable ageing time. The formation of Fe3O4 can be per-
formed under below the chemical reaction (Eq. (XI)):
Fe2 þ þ 2Fe3 þ þ8OH  -Fe3O4 þ4H2O
The reaction is mainly governed by adjusting the pH of the
solution; it is noteworthy to mention that magnetite can be
possibly obtained when solution pH is in the range of 8 to 14
along with Fe3 þ /Fe2 þ ratio equals to 2:1 under non-oxidizing
condition, based on the thermodynamics of reaction 33. Never-
theless, magnetite (Fe3O4) is very sensitive to oxygen presence and
tends to oxidize and transform into maghemite (γ-Fe2O3).
Fe3O4 þ2H þ -γ-Fe2O3 þ Fe2 þ þH2O
Magnetite is not the only compound undergoes the oxidation
in the presence of air; different electrons or ions also transfer by
changes in the pH of the suspension. As seen in Eq. (XII) iron ions
are desorbed from magnetite surface, creating cationic vacancies
and thereby lead to maghemite formation to keep balance of the
structure’s charge. Therefore, under basic conditions, the oxidation
of magnetite consists of the oxidation-reduction of the magnetite’s
surface. Magnetite differs from maghemite in terms of Fe ions
distribution in the octahedral and tetrahedral sites of the spinel
structure. Unlike magnetite, maghemite has cationic vacancies in
the octahedral site. The vacancies ordering is associated to the
synthesis method and results in symmetry lowering and possibly
superstructures. The vacancies can be either fully or partially
random or definitely ordered. It is necessary to mention that
vacancy ordering takes place only for particles exceeding 5 nm,
according to FTIR spectroscopy and X-ray diffraction results [87].
Fe3O4: [Fe3 þ ]Td [Fe3 þ Fe2 þ ]Oh O4
γ-Fe2O3: 0.75 [Fe 3þ þ
]Td [Fe35/3 V1/3]Oh O4
The coprecipitation technique takes advantage of fabrication of
the large amount of nanoparticles. However, since crystal growth is
controlled by kinetic factors only, particle size distribution cannot
be easily controlled. The coprecipitation process mechanism can be
divided into two phases [3,31,33,88]; first initial short nucleations
happens when the reactant’s concentration approaches the critical
super saturation, and second, gradual growth of the nuclei by
diffusion of the solutes to the surface of the crystal. To have
monodisperse iron oxide nanoparticles, the mentioned two steps
should be distinguished; it is recommended that no nucleation
should be taken place when crystal growth is being processed [89].
Moreover, size control of monodispersed-particles must usually be
performed during the first step, since the final particle number is
determined by the end of the nucleation and it does not change
during the growth step. Many various parameters can be modified
in the generation of iron oxide nanoparticles to control size,
magnetic and surface properties. The size and shape of iron oxide
nanoparticles can be customized by adjusting pH, ionic strength,
temperature, types of the salts (sulfates, nitrates, chlorides or
acetates), or ratio of Fe2 þ /Fe3 þ . Several studies have investigated
effect of important factors on generation of iron oxide nanoparticles
by coprecipitation method. For example the influence of the Fe2 þ /
Fe3 þ ratio on the morphology, size, and magnetic properties of
co-precipitated nanoscale particles were investigated by Jolivet [90].
Babes et al. [72] also investigated the effect of iron media and the
iron concentration. Regarding to their results, Fe2 þ /Fe3 þ molar
ratio is one of the key factors to obtain desirable size and yield
during the synthesis. In fact, increasing the molar ratio of Fe2 þ /Fe3 þ
causes enhancement in the mean size of the particles and decreases
the preparation yield. In addition, based on reports of literature,
particle mean size of magnetic particles also depends on the acidity
and the ionic strength of the precipitation agent [90–92]. Tartaj
et al. [93], reported that under high ionic strength and pH condi-
tions, smaller particle size and narrower size distribution will be
obtained.
(XI)
3.2. Hydrothermal method
Hydrothermal syntheses of magnetic nano iron oxide have
been investigated in the literature [94–102]. Hydrothermal
method is among the most well-known techniques of magnetite
generation where iron precursors in aqueous solution can be
heated at high temperature at autogenous pressure. In details,
reactions are carried out in aqueous media in stainless steel
autoclaves at high pressure and temperature. The temperature
(XII) and pressure can be above 200 1C and 2000 psi, respectively. This
technique can be processed through either hydrolysis and oxida-
tion or neutralization of mixed metal hydroxides which can lead
to ferrite formation. Synthesis of iron oxide by hydrolysis and
oxidation of ferrous salts in aqueous medium is more ordinary and
common [103]. During this process, parameters as temperature,
solvent, and reaction time normally play key roles in the formation
of final products [104]. For instance, larger sizes of Fe3O4 particles
were produced when higher water content exists in the reaction
set up. In the hydrothermal procedure, the particle size can be
controlled mostly by the rate of nucleation and crystal growth,
which contest for the species. Their particular rates is based upon
the reaction temperature while other conditions are kept constant
[105]. If the nucleation rate is faster than grain growth at higher
temperatures, it causes a reduction in particle size. However,
prolonging the reaction time would favor grain growth. Ferrite
nanoparticles with diameter of 27 nm have been synthesized and
revealed ferromagnetic properties by a hydrothermal route using
(XIII) surfactant, sodium bis(2-ethylhexyl)sulfosuccinate [104,106].
Another method to synthesize monodisperse iron oxide nano-
particles is thermal decomposition of iron organic precursors at high
temperatures. In this technique, iron precursors like iron pantacar-
bonyl and iron(III) acetylacetonate are applied along with organic
solvents and surfactants. A study on thermal decomposition of iron
oxide nanoparticles has been done using Fe(CO)5 with oleic acid
presence which resulted in highly crystalline and monodisperse
particles in the size range of 4–16 nm [107]. In addition, nanocrystal-
line magnetite was synthesized via the thermal decomposition
method applying iron choline citrate (C11H24FeNO11) by Gržeta
et al. [108]. Similar studies were also described using iron carbonate
[109] and carboxylate [110]. Fabrication of superparamagnetic
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
nanoparticles has been also reported by thermal decomposition
route using no solvent [111]. Liu et al. [112] have used solvothermal
route to prepare magnetic platelets applying ethylene diamine as a
reducing agent/solvent.
In hydrothermal method, size and shape of the nanoparticles
can be optimized by adjusting the reaction time, temperature,
reactants’ concentration and ratio, type of solvent, complexing
strength and precursors. Applying surfactants can assist to stabilize
the iron oxide nanoparticles and maintain the colloidal behavior of
the suspension. However, this process must be developed to be
appropriate for industrial scale-up, particularly in the case of high
temperature and reactant’s safety.
Hydrothermal method has been expanded by microwave techni-
que for superparamagnetic iron oxide nanoparticles lately [113]. The
advantage of this technique’s combination is to fabricate uniform-
sized superparamagnetic iron oxides nanoparticles and the ability to
scale up the process. Nanocrystalline magnetite was synthesized via
thermal decomposition method applying iron choline citrate (C11H24
FeNO11) by Gržeta et al. [114]. Similar studies were also described using
iron carbonate [115] and carboxylate [56]. Lately, Liu et al. [116]
synthesized magnetic platelets utilizing ethylene diamine as a redu-
cing agent/solvent by the solvothermal route. The solvent free thermal
decomposition method was also used for the generation of SPIONs,
recently [117].
3.3. Sol–gel method
The sol–gel rout is generally an appropriate chemical method
(wet) for the generating of metal oxides nanostructures [118–120].
This process includes the hydroxylation and condensation of
precursor in solution, originating a “sol” of nanometric particles.
Additional condensation and inorganic polymerization causes to
form a 3D metal oxide network termed as wet gel. Since the
reactions are performed at ambient, additional heat treatments are
required to obtain the final crystalline state [121,122]. It has to be
taken account that the gel’s properties strongly depend on the
structure formed within the sol stage. The key factors which affect
the kinetics, hydrolysis, growth reactions, condensation and thus
on the structure and characteristics of the gel are temperature,
solvent, precursors’ concentration, pH, agitation and nature of salt
[123–125].
For instance, γ-Fe2O3 nanoparticles have been obtained in a size
range of 6 to 15 nm by a direct heat treatment of the gels at a
temperature of 400 1C [126]. Sol–gel method proposed some
privileges such as [127] (i) fabricating tailor-made materials with
a predetermined structure based on the controllable experimental
process (ii) the capability to achieve pure amorphous phases,
monodispersity, and control of the particle size, (iii) the control of
the microstructure and the homogeneity of the reaction products,
(iv) the ability to implant molecules, which keep their properties
and stability within the sol–gel matrix and (v) utilizing low
temperature during materials processing. By sol–gel method,
γ-Fe2O3 nanoparticles can be placed in an inorganic, transparent,
inert, and temperature-resistant silica matrix [128–130]. Solinas
et al. [131] have prepared Fe2O3-SiO2 nanocomposites using differ-
ent molar ratios of Fe/Si in the range of 0.25–0.57 by the sol–gel
method. In this study, the effect of two parameters on the gelation
process was analyzed: the temperature and the surface of evapora-
tion/volume (S/V) ratio of the sol. This research implies that the
gelation process governs the formed nanoparticles’ size and phase
in the silica matrix. First, when a high S/V ratio is selected in the
gelation process, very small iron oxide particles are fabricated in the
nanocomposite because of the high porosity of the silica. In
contrast, the sols gelated with a lower S/V ratio, which conducts
to create large iron oxide particles. Second, low S/V values and high
temperatures in the gelation process lead to appearance of
213
maghemite, while high S/V values and low temperatures generate
the formation of hematite. Raileanu et al. [132] have prepared
nanocomposite of FexOy-SiO2 using alkoxide through sol–gel route.
Various precursors of silica were employed to investigate the
variations in structure and properties of synthesized nanoparticles.
The morphological and structural results obtained by XRD, TEM and
IR spectroscopy were in agreement with the magnetic properties
explored by Mossbauer spectroscopy.
3.4. Microemulsion technique
The microemulsion method is composed of three phases of oil,
water and surfactant. Microemulsions are transparent solutions
owning small droplets of an immiscible phase, non-polar or polar,
dispersed in a continuous phase (oil). The presence of surfactants
leads to decrease the surface tension between the continuous and
immiscible phases and keep the droplets stable. In other words, they
are responsible for micellisation which can disperse the obtained
iron oxide nanoparticles. Microemulsions can be either oil-in-water
or water-in-oil system which is subjected to the different compo-
nents’ concentration. Various concentrations of the surfactant and
dispersed phase, it is able to modify the droplets with sizes from 1 to
100 nm, roughly. Different self-assembled shapes and structures can
be fabricated such as spherical (inverted), lamellar phases, cylindrical
micelles and bicontinuous microemulsions, which may accompany
mainly aqueous or oil phases [133].
Inverse micelles and microemulsion route can be applied to
preparing the size- and shape- controlled iron oxide nanoparticles.
Geothite (α-FeOOH) nanorods were synthesized using ferric nitrate
in the presence surfactants at room temperature by Geng et al.
(2006). The obtained goethite nanorods were single-crystalline
with diameter of 8.271.5 nm and the length of 106716 nm.
Growth mechanism of α-FeOOH nanorods was introduced sug-
gested that the surfactant and high basic medium were key factors
in the directed growth of synthesized nanorods.
In addition to goethite, monodisperse maghemite was also
fabricated [134] through capping in the presence of a monolayer
coating of oleic acid. The results imply that a small size distribution in
the range of 3.570.6 nm and high saturation magnetization about
33.2 Am2 kg  1 for oleic acid coated nanoparticles were achieved.
Generation of magnetic iron oxide nanoparticles as small as 10 nm
and less was reported using water/oil microemulsion method by
Chin and Yacob. Furthermore, Chin and Yacob [77] claimed that
synthesized magnetic nanoparticles using microemulsion method
resulted in smaller particles compared to the particles synthesized by
Massart’s route [135]. Zhang et al. [107] prepared hollow iron oxide
nanoparticles with diameter in the range of 200–400 nm by the
microemulsion technique; but the obtained nanoparticles cannot be
applied for some purposes such as drug delivery systems. The
drawback of this method is rather poor crystalline superparamag-
netic iron oxide nanoparticles on a large scale because of the low
reaction temperature. Lee et al. [136] reported fabrication of crystal-
line maghemite particles in the nano-sized range by the microemul-
sion rout at high temperature using Fe(acac)3 as an iron precursor.
Another study by Sun and Zeng disclosed the synthesis of size-
controlled tiny magnetite nanoparticles (12–16 nm) using same iron
source by the microemulsion route [137]. It is noteworthy to mention
that despite the use of surfactants in the reaction, the aggregation of
the synthesized nanoparticles often requires further washing pro-
cesses and additional stabilization treatments.
3.5. Flow injection technique
Reaction zone confinement in different “matrixes”, such as
emulsions, etc., has been utilized to generate particles with small
214 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
size distributions and to change the particle morphology. Though,
a particular design of the reactor can act as a substitute to the
“matrix” confinement. Flow injection synthesis (FIS) method was a
novel method to generate magnetite nanoparticles represented by
Alvarez et al. [138]. This technique involves with continuous or
separated reagents mixture under a laminar flow regime within a
capillary reactor.
The FIS method enjoys several benefits, such as a high mixing
homogeneity, a high reproducibility due to the laminar conditions
and plug-flow, and a chance for accurate external control of the
process. The impact of chemical parameters and conditions on the
characteristics of the material was carried out. The synthesized
magnetite nanoparticles showed a small size distribution ranging
from 2 to 7 nm.
3.6. Aerosol/vapor method
Aerosol technologies are including laser and spray pyrolysis
which are interesting due to owning continuous chemical pro-
cesses permitting high rate production. Spray pyrolysis technique
consists of a set of reactors into which a solution of iron salts along
with reducing medium in organic solvent is sprayed, therefore the
aerosol solute condenses and the solvent evaporates [139]. The
obtained dried residue is composed of particles with sizes depends
on the size of the original droplets. Different shapes of maghemite
nanoparticles with size of 5 to 60 nm have been synthesized
applying different iron salts precursor in alcoholic medium [140].
In order to decrease the reaction volume laser pyrolysis technique
can be employed. In this technique laser is utilized to heat a
gaseous mixture of iron precursor which produce small size
nonaggregated particles. Similar to other techniques, adjusting
the experimental conditions may lead to obtaining maghemite
crystal size of 2 to 7 nm. For the gas-phase synthesis of nanopar-
ticles, laser pyrolysis as a tool is demonstrated with recent results
achieved in the preparation of iron-based mixtures and ethylene
as an energy-transfer agent are engaged with air as an oxidant
[87,141].
The characteristics of the product strongly depend on the main
process conditions. A study on the synthesis of Iron–carbon
nanoparticles utilizing laser pyrolysis obtained low mean size
core–shell nanoparticles (about 4–5 nm) with modified morphol-
ogies by increasing the ethylene flow. It is also observed that in the
synthesis of γ-iron oxide nanoparticles, low carbon contamination
can be achieved by ethylene evacuation under high pressure
condition. Generation and characterization of hybrid silica-iron
oxide composite microspheres have been reported by Julian-Lopez
et al. prepared using superparamagnetic nanoparticles for various
applications of hyperthermia, MRI and a hybrid mesoporous
matrix allowing the transport of bioactive molecules. These multi-
purpose products can be synthesized using spray drying a sol of
adjustable composition, enabling the control of the size and
amount of magnetic particles fixed in the matrix [142].
3.7. Sonochemical technique
The sonochemical technique has been widely applied to fabricate
novel materials with unique properties. The beneficial chemical
influence of ultrasound can lead to the formation of new phases
and highly monodispersive nanoparticles synthesis. Under high
temperature condition, salts can be converted to nanoparticles due
to the hot spot created by the rapid collapse of sonically caused
cavities. Sonochemical synthesis of nanosized hollow hematite was
disclosed by Bang and Suslick. In addition, pure magnetite nanopar-
ticles of 10 nm in size were generated using sonochemical route by
Vijayakumar et al. [143]. The measured magnetic properties showed
characteristics of superparamagnetizm for the synthesized Fe3O4
nanoparticles and very low magnetization at room temperature
(1.25 emu g  1). Lately, Pinkas et al. improved the sonochemical
technique using iron(III) acetylacetonate under Ar with a little
amount of water for the preparation of amorphous nanoscopic iron
oxide [144]. The specific surface area of the Fe2O3 nanoparticles can
be controlled by the amount of water added into the reaction
mixture. Enhancement in the specific surface area of the obtained
nanoparticles was observed from 48 to 260 m2 g  1. Abu and
Gedanken, have reported the formation of a stable hydrosol of
amorphous magnetite nanoparticles by the sonolysis of an aqueous
solution of iron pantacarbonyl using sodium dodecyl sulfate as
surfactant [145]. Sonochemical generation of iron oxide nanoparticles
by Kim et al. has led to obtain superparamagnetic and high crystal-
line particles [146]. Ferrofluids prepared from these nanoparticles
can be coated with oleic acid as a surfactant and the coated super-
paramagnetic iron oxide nanoparticles can be simply dispersed in
chitosan. The diameter of the cdinal particle after dispersion in
chitosan was calculated as 65 nm; particles also have shown very
good stability. Preparation of various iron oxide phases such as Fe,
Fe2O3, and Fe3O4 applying sonochemical technique has been done by
Kumar et al., and Shafi et al., as well [147,148]. Therefore sonochem-
ical method favors to prepare of monodisperse nanoparticles with
different morphologies and narrow sizes which can be considered as
an advantage. However, it is deficient in large scale production.
Considering all syntheses methods, the preparation process of
iron oxide nanoparticles has gone beyond the traditional routes
over time and has experienced a revolution. The main efforts have
been assigned to prepare multifunctional particles. Since instru-
mental advancements, characterization of particle size has been
much more comfortable which enable us to deep-understanding
of the nature of obtained products. In the matter of innovation,
novel techniques and reactants have been utilized to synthesize
nano iron oxides. The improvement has occurred from simple
precipitation to surfactant mediation, micro-emulsion, sol–gel,
emulsion and hydrothermal etc. methods, for synthesis of mono-
dispersed nanoparticles to apply in different functional platforms.
In terms of cost effectiveness for each synthetic procedure, it
would be respected to the final product and its application; for
example, in the case of drug delivery systems relatively higher cost
of manufacture is acceptable but when the product is supposed to
be used in water-waste purification to eliminate the toxic ions, it is
necessary to apply inexpensive chemicals [149].
4. Electrochemical synthesis of iron oxide nanoparticles
Electrochemical method has also been utilized to generate
different iron oxide nanoparticles phases like maghemite and
magnetite nanoparticles [150]. An electrochemical synthesis can
be basically interpreted by passing an electric current between
two or more electrodes which is called the anode and cathode
located in an electrolyte. In this technique, the anode can be
oxidized to metal ion species in the electrolyte and the metal ion is
later on reduced to metal by the cathode with the assistance of
stabilizers.
In fact, the synthesis occurs at the interface of electrode-
electrolyte. Here, several characteristics of electrosynthesis method
will be introduced which differentiate it from other generation
techniques. Electrochemical synthesis method occurs near to the
electrode in the electric double layer, owning high potential gradient
(105 V cm  1). According to these conditions, electrochemical reac-
tions usually give rise to products which is not possible to gain from a
chemical synthesis. The product is deposited on the electrode
normally in the form of a coating or a thin film. Additionally, a
solid–liquid interface favors the growth of coatings on substrates
with different morphology. Therefore, if a properly-shaped counter
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
electrode is applied, a uniform polarization is obtained. This method
doesn't require high temperature and should not exceed over the
electrolyte's boiling point. Kinetic control can be employed by
adjusting the current passed through the cell, even though thermo-
dynamic control can be applied by changing the cell potential. Since
electrochemical synthesis method is based on an oxidation/reduction
reaction, by altering and adjusting the cell potential, the oxidizing or/
and reducing power can be constantly fluctuated and appropriately
selected- which cannot be accessible by other methods in chemical
synthesis. The film structure can be controlled by changing the bath
composition and the experiments are effortless to run and the
instruments are cost effective and easily available.
Though, this technique has some disadvantages that must be
taken into account. Since reactions implement at room tempera-
ture, electrosynthesis technique often produces poorly ordered
products causes explicit structural characterization hard. X-ray
characterization of synthesized products usually shows amor-
phous impurities. Furthermore, electrodeposition is only able to
perform on conducting substrates. Nonetheless, the exclusive
characteristics of electrosynthesis enable it to be considered in
the “chimie douce” methods and suggest solutions to the chal-
lenge of producing metastable phases of iron oxide nanoparticles.
4.1. Design of Electrochemical synthesis
To have a successful electrosynthetic reaction, we need to make
a suitable choice of a reaction parameters listed as below:
(1) Possibility to choose inert or reactive electrodes
(2) Proper choice of electrolyte and its composition
(3) Suitable pH, temperature, electrolyte concentration
(4) Possibility of cells to be divided or undivided
(5) Electrolysis type: galvanostatic or potentiostatic
In an electrosynthesis reaction, obtained solid product typically is
the reactant which has been dissolved in the electrolyte. Accordingly,
the reactant activity declined as the reaction advances. The two key
factors that estimate the procedure of the reaction are the applied
current and the cell potential which both can be altered during the
reaction as a function of time.
In a typical galvanostatic synthesis an accurate control can be
performed over the reaction's rate, causing deposits with proper
adhesion and a modified morphology. Though, the cell potential
deviates by decreasing the reactant activity. The deviation in the
cell potential may form multiple products. A potentiostatic synth-
esis is composed of a three-electrode set up through polarizing the
electrode to a favored potential concerning a reference electrode.
As a result, the cell current reduces swiftly as the reaction
advances, because of decline in activity of reactants and low rates
of dispersal of the reactant molecules to the electrode surface.
Nevertheless, the reaction is apparently suitable to supply a pure
single-phase product by chosen potential.
In a typical potentiostatic synthesis, the actual potential to be
used is not just always known in advance. Thus, a linear voltam-
metry is actually first carried out by ramping the cell potential
from an initial value, Ei, to a final value Ef. Ei along with Ef
correspond to potentials where the solvent goes through electro-
lysis, in particular, the oxygen evolution and hydrogen evolution
potentials for an aqueous electrolyte solution. A potentiostatic
electrochemical synthesis can be executed if the reaction occurs at
any potential intermediate between these two values. When the
reaction potential drops outside the window provided by Ei and Ef,
then an appropriate electrode and solvent must be selected with
the suitable potential window including the reaction potential.
Fig. 3.
215
The separated cell really helps to separate the product of the
cathodic reaction from that of the anodic reaction and the
chemical composition of the product is governed by changing
the electrolyte composition.
In a real run, one or more of these synthetic key parameters
need to be practically chosen by implementing several different
trials, observing the product quality and yield.
The principles of electrosynthesis method reveal when electric
current is actually passing an electrolyte containing metal salt; the
metal is sedimented within the cathode. Current technique is
extensively utilized by plating technologists to fabricate metal
coatings. However, based on the applied potential, type of the
anion and the chosen pH of the solution, different reactions may
happen at the cathode [151]. The possible reactions are:
(1) The possible reactions that consume H þ ions like
(i) H þ þe  -Hads/abs
(ii) 2H þ þ2e  -H2 E1¼ 0.0V
(iii) NO3 þ2H þ þ2e  -NO2 þH2O E1¼0.934V
(iv) NO3 þ10H þ þ8e  -NH4þ þ3H2O
(2) In electrolysis of water
(v) 2H2O þ2e  -H2 þ2OH  E1 ¼ 0.828V
(3) In anion reduction reactions
(vi) NO3 þH2Oþ 2e  -NO2 þ2OH  E1¼0.01V
(vii) NO3 þ7H2Oþ8e  -NH4þ þ10OH 
4.2. Progress in electrochemical synthesis of iron oxide nanoparticles
A facile electrochemical method was suggested by M. Starowicz
et al., describing the synthesis of magnetic nanoparticles mostly
maghemite phase. The reaction was processed in LiCl solution in the
presence of ethanol and water [152]. The round shape nanoparticles
with an average size of between 5 and 40 nm were obtained which
was adjusted through water-to-ethanol ratio. Fig. 4 shows the TEM
images of magnetic nanoparticles synthesized by electrochemical
method. The deposits obtained at low concentration of water
(x¼3%) consist of very small needle-like nanoparticles as shown
in Fig. 4a. However, higher water concentration leads to a formation
of round-shaped nanoparticles of the size which can be controlled
just by water content in the solution. Fig. 4b–e shows the TEM
images of iron oxide nanoparticles with higher content of water
along with insets showing the size distribution of the produced
nanoparticles.
DC Power
Supply
Anode Cathode
Electrolyte solution
Magnetic bar
Magnetic stirrer
Heat Stir
Fig. 3. The typical electrochemical cell.
216 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
Fig. 4. TEM images of the deposit obtained in a course of Fe polarization in the solution: x  (0.1 M LiCl–H2O)þ (1  x)  (0.1 M LiCl–C2H5OH) for (a) x¼ 3%, (b) x ¼5%,
(c) x ¼15%, (d) x ¼50% and (e) x ¼ 100% (adopted from [152]).
Magnetisation measurements for the samples obtained at 50% and
100% water content are shown in Fig. 5. Hysteresis loops measured at
four temperatures from the range 10, 100, 200 and 300 K and at the
magnetic field varying between þ89 and  89 kOe. The saturation
magnetization measured at 10 K and 89 kOe amounts to 35.5 emu g  1
for the sample obtained at x¼50% (particle size 10–20 nm) and
50.9 emu g  1 for the sample obtained at x¼100% (particle size of
20–40 nm) which is much smaller than 91.5 emu g  1 compared to
nanocrystalline magnetite of 37 nm particle size reported by Ozdemir
et al. [153].
D. Gopi et al. reported electrochemical synthesis of super-
paramagnetic cubic magnetite nanoparticles (MNPs). The cubic
magnetite nanoparticles have been generated by electro-oxidation
of iron in aqueous medium of ferrous perchlorate. This results in
uniform particles with the size of 15 76 nm. These results show
the possibility of surface plasmon resonance effect in the iron
oxide nano particles while no micelles or stabilizing agent or
surfactant was applied to avoid formation of cluster growth [154].
Fig. 6a–c shows the low and high magnification TEM images of
cubic magnetic nanoparticles which were electrochemically
synthesized in 0.1 M Fe(ClO4)2 at 50 mA cm  2.
A vibrating sample magnetometer spectrum was also recorded
for magnetite nanoparticles synthesized by electrochemical
method at 0.1 M concentration of Fe(ClO4)2 at 50 mA cm  2. The
hysteresis curve demonstrates the superparamagnetic property of
the magnetite nanoparticles at room temperature and it shows a
very less coercive field (50 G). The applied magnetic field is in the
range of  15,000 to 15,000 Gauss while the magnetization is not
saturated in this applied magnetic field which is terminated at
27 emu g  1. Fig. 7.
C. Pascal et al. studied the generation of γ-Fe2O3 nanoparticles
with an electrochemical method using an organic medium. The
particle size was instantly supervised by the employed current
density. In addition, use of cationic surfactants resulted in enhan-
cing the stability of the particles which led to formation of
colloidal suspension. The average particles ranging in 3–8 nm
caused a narrow particle size distribution. Mossbauer spectro-
scopy and magnetization measurements displayed that the nano-
powders possess superparamagnetic property at ambient [150].
S. Franger et al. reported pure, homogeneous and ultrafine
magnetite particles synthesized by the electrochemical technique
at ambient using a Fe electrode which was submerged in an
alkaline medium consisting of complexing compounds. The pure
magnetite, Fe3O4, shows a magneto-resistance of approx. 3%,
subject to a magnetic field of 1 T, at 300 K. The complexing agents
were utilized to enhance the charge transfer kinetics and assist to
decline the size of obtained particles to nano scale [155].
Fe3O4 nanoparticles were prepared through a novel process
originated from electro-precipitation in ethanol by M. Ibrahim
et al. [147]. Fig. 8 shows the TEM images representing that
particles have an average mean size centered on 6.2 nm with a
quite narrow distribution. However, nanoparticles have shown
strong tendency towards the agglomeration due to the free-
surfactant production.
4.3. Formation mechanism
The mechanism of generation of iron oxide particles by electro-
precipitation can be explained in a way that iron(III) ions are
reduced at the cathode into iron(II) with potential in the range of
0 to 1 V/ref. These iron(II) ions deposit on the cathode into
magnetite nanoparticles only in the presence of ethanolic medium
which carries water and nitrates. However, if there is too much
water content, hydroxide will be formed and cannot have magne-
tite anymore. Under high current density, the magnetite nanopar-
ticles can be produced. When current density is low, water and
nitrates cannot be reduced based on cyclic voltametric proof. Iron
(III) ions are easily reduced into Iron(II), but the insufficient pH
(not too high) at the cathode does not have a tendency to deposit
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
Fig. 5. Magnetization curves (magnetization vs. applied field) for the sample
obtained at (a) x ¼ 50% and (b) x ¼ 100%. The insets show hysteresis loops (Adopted
from [152]).
Fe3O4 nanoparticles. Therefore, Iron(II) drifts to the anode to have
reoxidation. When the solution contains Iron(III), nitrate ions and
water under high current density, whole of the current is utilized for
reduction of Iron(III) ions initially, but gently decreases during the
electro-precipitation process as the formation of magnetite nanopar-
ticles increases. It is assumed that the passivation electrode phenom-
enon prohibits the Fe3O4 nanoparticles. The proposed mechanism
based on the experimental results for synthesis of Fe3O4 nanoparti-
cles by electro-precipitation route can be explained as following:
– Reduction of water and nitrates generates the OH  ions at the
cathode:
(i) NO3 þH2Oþ 2e  -NO2 þ 2OH 
(ii) 2H2O þ2e  -H2 þ 2OH 
The pH enhances near the cathode and leads to Fe(OH)3 to
precipitate. Then, the Fe(OH)3 is reduced to magnetite
(Fe3O4) based on the reaction comes below:
(iii) 3Fe(OH)3 þ e  -Fe3O4 þ4H2Oþ OH 
This should be taken into account that reaction (3) re-produces
the water, which was applied in reduction of water and nitrate
ions. Note also, reaction (3) is an equilibrium, representing that
magnetite nanoparticles are not produced due to extra water
217
existence in the solution, and Fe(OH)3 continues to possess stable
[156].
It is noteworthy to mention that formation of magnetite
nanoparticles by electrochemical method is usually associated
with changes in color of the reaction solution. At the beginning
of the experience, when no i or E was imposed, the solution was
colorless. As the reaction takes place, the solution color turns
brown-red, and subsequently it changes to black indicating the
formation of magnetite. The UV spectrum of the initial brown
color solution corresponds to ferric hydroxide while the spectrum
for the final black solution corresponds to magnetite. In iron
electrooxidation similar reactions can be also taken placed. At
the beginning of the reaction, at the anode, iron was oxidized first
to ferrous ions and then to ferric ions due to high i or E imposed:
(1) Fe3 Fe2 þ þ 2e 
(2) Fe2 þ 3 Fe3 þ þ1e 
Another reaction that takes place and provides protons to the
proximities of the anode is the electrolysis of water according
to reaction:
(3) H2O 3 2H þ þ2e  þ 1/2O2
At the cathode the reduction of water takes place as presented
in Eq. (II). Since pH of the solution was not initially high but
increases during Eq. (II), the precipitation of ferric ions as
hydroxide is favoured and precipitation of ferric hydroxide
(brown solution) occurs during the first minutes of process
following reaction (4):
(4) Fe3 þ þOH  3 Fe(OH)3(s)
The OH  ions produced at the cathode (2) arrive to the
anode’s surface by diffusion, proportioning the basic medium
necessary for the iron hydroxide to be formed. Ferric hydro-
xide can now react in two different ways. If the pH of the
solution is not basic enough, it may dehydrate to generate a
non-magnetic ferric oxide. However, if the pH is around 8 or 9,
ferric hydroxide can be reduced at the cathode to form Fe3O4
as represented in the following equation [156]:
(5) 3Fe(OH)3(s) þH þ þe  3 Fe3O4(s)þ 5H2O
4.4. Key parameters in electrochemical synthesis of iron oxide
nanoparticles
One of the most important factors in the production of iron
oxide particles (Fe3O4) by electrooxidation is the distance between
two electrodes of anode and cathode. Since, hydroxyl ions (OH  )
which were produced at the cathode are required to reach to the
anode's surface due to the formation of iron hydroxide, the
distance between the anode and cathode matters. L. Cabrera
et al. [157] reported that if the distance between the anode and
cathode is greatly enhanced, the interface near to the anode would
not reach the necessary pH value to form the iron hydroxide. Even
if the hydroxide is formed, it would not be reduced at the cathode,
at least not in an appreciable amount. Therefore, when the
electrode distance was larger than 5 cm, electrogeneration of
magnetite was not observed during the standard reaction time
obtaining on the contrary a mixture of hematite and goethite, both
non-magnetic.
Another key factor in the synthesis of magnetite particles is the
imposed current density during the electrochemical process. It is
claimed that the amount of magnetite precipitate improves with
the increasing in the current density values [158]. K. G. Chan-
drappa et al. reported the successful preparation of nanocrystalline
magnetite and hematite through hybrid electrochemical-thermal
method. Different concentrations of electrolyte, 30, 60, and
120 mM of sodium bicarbonate were applied in Millipore water
at pH of 8.5 [159].
218 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229

Fig. 6. TEM image of (a) MNP electrochemically synthesized in 0.1 M Fe(ClO4)2 at 50 mA cm  2 (b) its high resolution images at 20 nm (c) at 2 nm and (d) its selected area
electron diffraction pattern (adopted from [153]).

Fig. 7. Hysteresis curve of as-synthesized MNP from 0.1M of Fe(ClO4)2 at

50 mA cm  2 (adopted from [153]).

4.5. Electrochemical synthesis of other metal oxides nanoparticles

NiO nanoparticles were produced through an electrochemical
route modeled after the procedures of Reetz et al. [160]. Reetz
produced both Ni and Pd nanoclusters of dimensions between
2.2 and 4.8 nm. CuO [161] and ZnO [162] nanoparticles have been
prepared through electrochemical methods in the manner of Reetz
et al. [160].
Fig. 8. TEM photograph for typical Fe3O4 nanoparticles. Experimental conditions:
Fe(NO3)3  9H2O¼ 2  10  2 M in ethanol, 30 mA cm  2 (adopted from [147]).
Thick micrometer-sized films of Cu2O have been electrodepos-
ited within an alkaline solution of C6H10O6Cu (cupric lactate) using
a precise potential or current. Firstly composite of Cu/Cu2O and
consequently Cu deposition were formed [163]. By variation in
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
reaction conditions in order to gain nanocomposites of Cu/Cu2O, a
shifting in the band gap of Cu2O was observed from the value of
2.1 eV corresponding to the bulk counterpart to value of 2.5 eV.
Moreover, an intense growth in the absorption coefficient was
evident which arises by quantum confinement effects [164].
Compositionally nano-scaled layer-by-layer deposits in the Pb-Tl-
O system have been electrosynthesized by pulsed deposition
[165,166] and STM (scanning tunneling microscopy) technique
was applied to determine the deposit’s corrugation. G. Ali et al.
reported a straightforward and facile strategy to prepare TiO2
nanoparticles by electrochemical anodization using a titanium
wire in an aqueous potassium chloride electrolyte. The size of
the fabricated nanoparticles could be simply modified by adjusting
the electrolyte concentration [167].
ZnO microstructures were developed by electrochemical route
and various shapes and morphologies were obtained, including nest,
petal, sphere, flower and clew aggregates at ambient conditions
[168]. M. Starowiczet al. also reported electrochemical synthesis of
ZnO nanoparticles [169]. Electrochemical self-assembly generation of
ZnO nanoparticles was investigated in an anionic surfactant solution
by H. Usui [170]. Chromium oxide (Cr2O3) nanoparticles were
generated by utilizing an electrochemical method by S. Rakesh
et al. The Cr2O3 nanoparticles showed enhanced the antibacterial
effect against E. coli [171]. Different phases (MnO, MnO2 and Mn3O4)
of nano manganese oxide materials in the average size range of 21 to
40 nm were generated applying electrochemical method by S.
Thiagarajan et al. [172].
Well-ordered structures of various oxides and chalcogenides
including CdTe, CdSe, CdS, ZnO, ZnSe, Tl2O3, PbO2, Cu2O, δ-BiO3,
Fe3O4, PbSe and PbS) have been synthesized by electrochemical
epitaxy on metallic substrates (platinum and gold) or crystalline
TiO2, Si, InP, GaAs, GaN [173].
5. Surfactant-free synthesis of iron oxide nanoparticles
Several studies on surfactant-free method for synthesizing
magnetite nanoparticles using liquid phase reactions have been
reported [174,175]. Nishio et al. prepared magnetite nanoparticles
by oxidizing ferrous hydroxide with a weak oxidant in an
N2-deaerated aqueous NaOH solution at various temperatures
below 37 1C without any surfactant [174]. The particles produced
by their method had sizes in the range of 30–100 nm in respect to
the synthesis temperature. Ahniyaz et al. synthesized magnetite
nanocrystals by thermal decomposition of iron alkoxide precur-
sors without surfactant at temperatures higher than 320 1C result-
ing nanocrystals with an average size of approximately 5.6 nm
[175]. Their method involved the use of organic solvents such as
octadecene and ethanol that may remain on the particle surface
and tend to make the particles to be hydrophobic. It has been
Fig. 9. Different structures of coated iron oxide.
219
shown that, as illustrated by the Pourbaix diagram, magnetite,
hematite, iron(II) and iron(III) hydroxide can be in electrochemical
equilibrium with water at high potentials in basic and neutral
solutions [176]. Therefore, an iron oxide film may be grown
electrochemically on the surface of iron-based materials to pro-
duce a blue-black layer, a light brown oxide, or a semi-adherent
Fe3O4 layer by varying temperature, voltage, and electrolyte
composition [177]. It is noted that if an iron film layer coheres to
an anode surface, iron oxide would be generated from the surface
due to the electro-oxidation and unlike the iron film would not
cohere to the surface. In the basic aqueous medium, Fe3O4 may be
produced by the corrosion process [178]. The particle size might be
constrained by controlling the current density of the system,
which controls the oxidation rate. F. Fajaroh et al. [179] reported
on the electrochemical synthesis of nano-sized particles of mag-
netite using a sacrificial iron anode and untreated water as the
electrolyte without any surfactant. The magnetite nanoparticles
produced are nearly spherical and are uniform in size, with mean
sizes ranging from about 10 to 30 nm based on the experimental
conditions. Although there are some impurities in the form of iron
oxy-hydroxy, which is a non-magnetic material, the nanoparticles
still demonstrate ferromagnetic behavior with comparatively high
saturation magnetism.
6. Surface modification of iron oxide nanoparticles
6.1. Surface modification of iron oxide nanoparticles by organic
materials
Term stability is the most important parameter of ferrofluids
during both synthesis and storage. Organic compounds are usually
used to passivate the iron oxide nanoparticle's surface within the
preparation process and afterwards to prevent agglomeration.
Regarding to iron oxide nanoparticles, application of a suitable
surface coating is inevitable. This can be explained by character-
istics of iron oxide nanoparticles, which possess hydrophobic
surfaces along with large specific surface area-to-volume ratio,
which give rise to aggregation and large cluster formation and
finally enhancing the particle size. [180].
Recently, significant attentions have been assigned to the
design and controlled synthesis of nanomaterials representing
particular functional characteristics. Organic compounds coated
on iron oxide nanoparticles propose an increased potential appli-
cation in many various areas. The structure of organic compounds
which are supposed to functionalize magnetic iron oxide nano-
particles is composed of two main sections: maintaining the
magnetic property of magnetic iron oxides simultaneously with
keeping the properties of organic molecules. In coating procedure,
iron oxides are often considered as core; therefore the proposed
220 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
structure can approximately be categorized into three kinds of
shella–core–shellb, core–shell and matrix as seen in Fig. 9. Gen-
erally, coating of various phases of iron oxide nanoparticles by
organic material provides core–shell nanostructure. In these types
of structures, the cores can be any type of iron oxide particles,
including maghemite, magnetite, magnetite etc. Similarly, the
shells can also contain any type of materials among organic ones.
Besides, matrix structure consists of two common structures,
shell–core and mosaic. The shell–core structure owns the organic
compound nanoparticles as core and iron oxide nanoparticles as
shells. The connection of iron oxide nanoparticles with the organic
core may take place through chemical interactions. The mosaic
structure can be described as a shell layer of organic molecules
which is coated on a large number of steady iron oxide magnetic
nanoparticles. Polymers because of their unique characteristics are
appropriate candidates to be applied to accommodate the nano-
particles. In the case of shella–core–shellb structure, it goes beyond
and a shell layer of organic molecules is coated to a shell–core
which is focus of many studies nowadays and normally fabricated
by layer-by-layer method. The shella and shellb both can be made
of either polymer/biomolecules or different functional materials.
Additionally, conductive organic material with multiple compo-
nents along with iron oxide nanoparticles can be customized to
prepare favorite mechanical, optical and electrical properties.
Iron oxide nanoparticles surface modification; using organic
compounds not only furnish the basic magnetic properties of
obtained nanoparticles, but also own good biodegradability and
biocompatibility. Furthermore, organic materials can equip the func-
tional reactive group like hydroxyl, aldehyde, amino and carboxyl
groups. It is essential these functional groups connect to the active
biomaterial including protein, DNA, antibody, enzyme etc. The
subsections below ascribe different organic materials, including
surfactants, polymers and biological molecules which are commonly
used to functionalize iron oxide nanoparticles.
6.1.1. Surfactants
As mentioned in the previous section, to avoid agglomerations
and achieve iron oxide suspension with desirable stability, exis-
tence of a proper surface functionalization and solvent are essen-
tial. In fact presence of surface functionalization assists to create
enough repulsive interactions which lead to reduction or absence
of particles agglomeration. Surface active agents or surfactants are
one of the commonly used materials to modify the nanomaterials
surface. These small organic molecules can be directly categorized
into three groups: water-soluble, oil-soluble, and amphiphilic.
Water-soluble surfactants are considered as organic compounds
contain the hydrophilic chemical groups with a strong attraction
for the solvent environment, like polyol, ammonium salt and
lycine. In contrast, Oil-soluble category may refer to the surface-
functional materials consisting of the hydrophobic molecular
group with a weak attraction towards the solvent environment,
including alkyl phenol and fatty acid. Finally, amphiphilic group
represents materials that possess both hydrophobic and hydro-
philic chemical groups. Theses surfactants’ major chain indicated
compromise of hydrophilic and hydrophobic regions, which cause
the functionalized nanoparticles, own both water- and oil-solubi-
lity, respectively.
Oil-soluble surfactants usually applied to avoid or decline the
agglomeration of iron oxide nanoparticles and enhance their
stability which leads to the monodispersity. To give some exam-
ples, hexadecane which has been regularly used to disperse the
iron oxide nanoparticles or the famous oleic acid with long tail
containing C¼ C bond which indicated strong effective ability to
disperse the nanoparticles. However, stearic acid with the same
long tail, but no carbon double-bond, did not play an effective role
in stabilization [181–184]. Furthermore, Oleic acid is extensively
utilized in the synthesis of ferrite nanoparticles due to its ability to
build a dense protective monolayer can bring high uniformity and
monodispersity. Comparatively speaking functionalized iron oxide
nanoparticles showed the enhancement in the mean diameter of
particles ranging from 0 to 5 nm, while their saturation magneti-
zation roughly remains unchanged.
Several studies have been investigated the generation of
magnetic iron oxide nanoparticles using oil-soluble surfactants.
Surface-coated magnetite nanoparticles have been synthesized
by Shaoo et al. [185] using lauric acid, oleic acid, dihexadecyl
phosphate, hexadecyl phosphonate and dodecyl phosphonate.
Magnetic nanostructures with mean size of 6–8 nm could be
obtained owning high thermodynamic stability. It is assumed that
ligands of organic species may construct a quasi-bilayer structure
firmly bound to the surface of the nanoparticles. From the results,
this can be concluded that alkyl phosphates and phosphonates
attached effectively to the surface of iron oxide nanostructures. In
addition, phosphates and phosphonates ligands which possess
good biocompatibility may improve the application of encapsu-
lated magnetic nanostructures in the medical industry including
MRI and biophysical targets. The synthesis of capped ultrafine
maghemite nanoparticles by the thermal treatment of a Fe(OH)3
and using caprylate gel under vacuum conditions have been
reported by Bourlions et al. [186]. The capped spherical nanopar-
ticles with mean size of 4 nm, were simply dispersed in organic
solvents to govern homogeneous and stable magnetic particles.
Surface functionalization of the iron oxide nanoparticles using
oil-soluble surfactants are simple and controllable to some extent
while presently the synthesis and control of iron oxide nanopar-
ticles utilizing water-soluble surfactants with expected character-
istics of high dispersity in aqueous solution, biological compa-
tibility, low cytotoxicity and biodegradability is the most impor-
tant controversial issue. Iron oxide nanoparticles, which are
functionalized by water-soluble surfactants, have shown a broad
potential application scope in bio-detection and bio-separation.
In order to synthesize functionalized iron oxide nanoparticles
applying water-soluble surfactants, a number of methods can be
utilized. One route is adding the biocompatible surfactant like
cyclodextrin [187–189], vitamin [190,191], citric acid [185,192],
amino acid [193] etc. straightaway within the synthesis procedure.
Lately Xia et al. [194] described a novel synthesis of magnetite
nanoparticles using cyclodextrin (CD) nonylphenyl ether (NP5)
and polyethylene glycol (PEG) as water-soluble surfactants in the
aqueous medium. Further, spherical nanostructured aggregations
were obtained from individual core–shell nanoparticles which can
be modified by drifting the surfactant concentration. These meso-
porous aggregations of magnetite iron oxide nanoparticles can be
applied in the magnetic carrier method. Although the mentioned
method (direct) has some benefits, do not represent high stability
due to its small organic molecules, particularly in the alkaline
and/or acidic medium, it usually breaks down and terminates in
the agglomeration of functionalized iron oxide nanostructures. In
addition, the morphology of functionalized iron oxide nanoparti-
cles normally appears as agglomerate clusters.
There is another route able to change the oil-soluble functio-
nalized iron oxide nanoparticles into the water-soluble one, and
the reaction of ligand-exchange is the main procedure to under-
stand this purpose [195]. For adjusting the surface properties of
nanoparticles, ligand exchange is a famous technique. It includes
addition of an increase of ligand to the nanoparticles’ solution,
which leads to the replacement of the primary ligand on the
nanoparticles’ surface. Particularly, ligand-exchange reactions on
noble metal nanoparticles, through the self-assembly of thiols,
have been utilized for a long time [196,197]. Though, lately, many
studies have been investigated the surface properties of iron oxide
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
nanoparticles applying ligand exchange technique. In particular,
Sun et al. [137] have reported preparation of monodispersed Fe3O4
nanoparticles with adjustable diameter in the range of 3–20 nm at
high temperature using iron(III) acetylacetonate, in the presence of
oleic acid, oleylamine and 1,2-hexadecanediol. Indeed, the hydro-
phobic property of nanoparticles can be changed into hydrophilic
ones through blending with bipolar surfactants like tetramethy-
lammonium 11-aminoundecanoate, leading to synthesis of aqu-
eous dispersions of nanoparticles. Moreover, Hatton and Lattuada
[198] reported that the oleic groups primarily appear on the above
nanoparticles’ surfaces were displaced through ligand-exchange
reaction with different capping agents carrying reactive hydroxyl
species. Additionally, they claimed that particles with the size of
6 to 11 nm can be modified with no seeded-growth procedure by
easily drifting the solution’s heating rate owning the nucleating
particles. This technique suggests a flexible methodology for the
fabrication of different sort of water-soluble, monodisperse mag-
netic nanostructures coated by various polymer brushes. Similarly,
Fan et al. [199] prepared maghemite nanoparticles dispersed in
water indicating narrow size distributions of 13 72 nm through
ligand-exchange reaction, which led to obtain stable and super-
paramagnetic particles with no agglomeration in a broad range of
pH 3–9. Nevertheless, the ligand-exchange reaction frequently
provides complex operations and the exchange rate’s control
difficulties, these obstacles need to be overcome. Additionally,
silane agents are normally believed as a good candidate for the
surface modification of iron oxide nanoparticles, due to the
privileges such as high density of functional groups, biocompat-
ibility, and ability to easily link to other metal, biomolecules
and polymer [200,201]. Besides, silane-coated iron oxide nano-
particles still preserve the physical properties of unmodified
nanoparticles; only a small decline in the saturation magnetization
about 10 emu g  1 and less may be observed. The physic-chemical
mechanism of iron oxide nanoparticles modified by silane agents is
explained in details by Arkles [202]. Accordingly, the methoxy groups
of the silane agents are believed to react with hydroxyl groups on the
surface of iron oxide nanoparticles results in the Si–O bond formation
allowing the immobilization of the other substance. W. Wu et al.
prepared Fe3O4 nanoparticles possessing average diameter of
2575 nm using moderated co-precipitation technique, applying
silane agents to approach amino- and thiolated-coated Fe3O4 nano-
particles through APTES (3-amino propyl triethyloxysilane) and
MPTES (mercapto propyl triethoxysilane) modification. The result
indicates that the average diameter of surface functionalized mag-
netic nanoparticles slightly increased while primary saturation
magnetization was roughly maintained; APTES tends to preserve
the morphology of the magnetite nanoparticles, but MPTES shows a
significant hypochromic impact, although it permitted to a small
decrease in the saturation magnetization. These discoveries have a
considerable importance due to the direct relative to applications
such as biosensing, target carriers and bioconjugation [180]. Further,
silanes are able to make the iron oxide nanoparticles water-
dispersible and highly stable, and form preservative layer versus
mild alkaline and acid medium.
Different surfactants have been employed in the synthesizing
of nanoparticles such as cetyltrimethyl ammonium bromide
(CTAB), sodium dodecyl sulfate (SDS), bis(2-ethylhexyl) sulfosuc-
cinate (AOT), polyvinyl pyrrolidone (PVP) and diethyl sulfosucci-
nate (DES) [203–205]. In this study, the effect of PVP, saccharin,
SDS, glycerol, CTAB and triton X-114 was investigated on the
particle size and morphology of iron oxide nanoparticles. For a
selection of suitable additives, several synthesizes were processed
using different additives with the same concentration (5 g L  1).
Initial experiments showed that PVP, SDS and glycerol are
not suitable as additives in magnetite electrosynthesis. These
additives are made to extremely decrease the rate of nanomagnetite
221
synthesis. CTAB acts better than the PVP, SDS and glycerol. In the
presence of CTAB, the sample includes uniform nanorods. At
the next step, the effects of CTAB concentration were studied on
the sample morphology. By using 1 g L  1 CTAB in 2 M potassium
hydroxide solution, a sample containing uniform nanorods can be
synthesized. Therefore 1 g L  1 CTAB is suitable to control the
formation of magnetite nanorods. CTAB in 2 M potassium hydroxide
solution converts homogeneously into cetyltrimethyl amine and
potassium chloride. The formed cetyltrimethyl amine acts as a
suitable complex agent to stabilize iron ions (Fe2 þ and Fe3 þ ). The
complex formation can change kinetics and the mechanism of a
magnetite formation [206].
6.1.2. Polymers
Even though quite a few studies’ concentration have been
directed to the advancement of small organic molecules coating
(surfactants) so far, polymers have been recently attracted so
much attention due to their unique properties. First of all, polymer
coating can be enhanced the repulsive forces to steady the van der
Waals and the magnetic attractive forces existing on the nano-
particles. Secondly, polymer surface coating makes iron oxide
nanoparticles a potential candidate in the several application
fields, and finally polymers possess very flexible and exclusive
physical and chemical characteristics. Employing polymeric mate-
rials for basic or applied research requires availability of well-
defined nanoparticles, which their properties can be drifted using
chemical modifications. Several studies have reported that under
particular reaction conditions and proper use of the activating or
passivating polymers, nanoparticles with favorable properties can
be produced.
Two main categories of polymer materials used to coat iron
oxide nanoparticles are natural and synthetic. The main drawback
of polymers’ utilization in functionalized iron oxide nanoparticles
is the reduction in the saturation magnetization value of obtained
particles. Presently, there are two principal advancing purposes to
produce polymer-functionalized iron oxide nanoparticles; first is
to extend the applications by functional iron oxide nanoparticles
using polymers. Accordingly, poly ethyleneglycol-modified (PEG)
superparamagnetic iron oxide nanoparticles were prepared utiliz-
ing the microemulsion polymerization technique by Gupta et al.
[207]. Core–shell magnetic particles consist of hydrophilic poly-
meric shell and magnetic core. The mean size of the PEG-modified
nanoparticles was measured to be about 40–50 nm indicating
small size distribution. The cytotoxicity test of the modified
nanoparticles on human dermal fibroblasts proves that the nano-
particles are not only toxic but also suitable for different in vitro
and in vivo biomedical applications. Second purpose can be
described as generation of monodisperse nanoparticles possessing
well-defined morphology and enhanced properties. To obtain the
uniform magnetic nanocomposites monomer polymerization
technique or method using microporous polymeric microspheres
were employed [208]. An attempt has been done to apply polymer
micro-gels as template for the preparation of iron oxide particles
by Zhang et al. [209]. Initially, precursor cations were unified into
the poly(N-isopropyl acrylamide-acrylic acid-2-hydroxyethyl acry-
late) microgel particles bonded with N,N0 -methylene bisacryla-
mide (BIS), then iron oxide nanoparticles were formed in the
microgel by co-precipitation. They represent that nanoparticles
with predefined dimensions and size-dependent characteristics
can be prepared utilizing elegant equilibrium among the composi-
tion, the reaction conditions and the microgel templates’ structure,
nanoparticles’ concentration.
The fabrication of superparamagnetic magnetite nanoparticles
using the microgel templates was strongly effectual: when con-
centrations of the nanoparticles were high enough as 0.724 g per
222 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
1 g polymer, the nanoparticles showed the mean size of 8 nm,
strong magnetic properties and low dispersity whereas the micro-
spheres bearing these nanoparticles stayed stimuli-responsive.
Moreover, another method of atom transfer radical polymerization
(ATRP) was utilized for synthesizing well-defined monodispersed
nanoparticles with the shape of core–shell. ATRP can propose low
polydisperse polymeric shells and current technique is facile
for controlling the molecular weight, therefore, the shell’s thick-
ness. Several polymer-coated iron oxide nanoparticles were lately
improved using surface-initiated ATRP in polar solvents [210–212].
This technique can be applied in polymers preparation with
relatively narrow molecular weight distribution, random copoly-
mers, block copolymers graft polymers, and eventually to tune the
polymeric shell’s thickness and the size of obtained nanoparticles.
Sun et al. [213] have successfully prepared the core/shell iron
oxide nanoparticles using polystyrene via surface initiated ATRP.
The procedure was initially started through a technique in which
initiators can bond covalently onto the iron oxide nanoparticles’
surface, that was the incorporation of ligands exchange reaction
and condensation of triethoxysilane having an ATRP initiating site,
2-bromo-2-methyl-N-(3-(triethoxysilyl)propyl) propanamide, fol-
lowed by grafting the polystyrene shell from the primary sites on
the iron oxide surface by ATRP. The advantage of covalent-bonded
polymeric shell is to avoid unwanted site-exchanging of function-
alities on the surface of the magnetic nanoparticles.
Furthermore, polymers are regularly applied to compensate the
insufficiency of small organic molecules and surfactant to obtain
the surface functionalized iron nanoparticles oxide. However,
preparation of the functionalized iron oxide nanoparticles with
good biocompatibility and ideal chemical stability are still
addressed as the main challenges. The correct choice of organic
materials, supplies a structure appropriate for preparing the well-
controlled functionalized nanoparticles. Frankamp et al. [214,215]
advanced a route for control of the magnetic interaction between
iron oxide nanoparticles using self-assembly phenomenon of
dendrimer. The obtained assemblies promote the enhancement
of the interparticle spacing which exceeds 2.4 nm with boosting
the dendrimer generation. This rise in spacing moderated the
collective magnetic behavior by the effectual decreasing in the
dipolar coupling among the particles. In conclusion, the advance-
ment of other techniques for fabrication of the surface-modified
iron oxide nanoparticles are of great interest and still questionable.
6.1.3. Biological molecules
A variety of biological materials, including avidin and biotin
[216], antibody [217,218], peptides [219], protein [220] etc. have
been chemically linked to the surface of iron oxide nanoparticles
either directly or indirectly through some functional. The iron
oxide nanoparticles functionalized by biological materials will
considerably show biocompatible property. Such target specific
magnetic nanoparticles are useful to effectually separation of
biochemical materials such as cells, DNA, proteins etc. A human
serum albumin (HAS)-coated magnetite particles with diameter of
200 nm were prepared as a radioisotope carrier using microemul-
sion technique by Zhang et al. [221].
The common approach for surface functionalization of nano-
particles by biomolecules involves two stages; primary synthesis
of the small molecules or polymer-functionalized nanoparticles,
and secondly the obtained functionalized nanoparticles can be
coupled to the biological molecules through physical adsorption or
chemical bond. Lately, Lee et al. [105] improved a method for
intermixing the maghemite nanoparticles and single strand oligo-
nucleotides. The water-soluble magnetic nanoparticles containing
carboxyl groups on their surfaces were synthesized firstly, and
then by applying 1-ethyl-3-(3-dimrthylaminopropyl) carbodiimide
hydrochloride (EDC) as a reagent, they could tune streptavidin, a
protein, on the surface of maghemite nanoparticles. Streptavidin
functionalized-maghemite can gain biotin-labeled single strand
oligonucleotides within the robust affinity between biotin and
streptavidin.
Further, individual nanoparticles with superparamagnetic iron
oxide core yields effectively within the dephasing the protons’ spins
of surrounding water, increasing spin-spin relaxation times (T2) in a
way that the nanoparticles implement as magnetic relaxation
switches (MRS) [222]. In regards to this phenomenon, Perez et al.
[223] have lately prepared biocompatible magnetic nano-sensors
that function like MRS to diagnose molecular interactions in the
reversible self-assembly of disperse magnetic particles in stable
nano assemblies. MRS technique may be applied to discover various
kinds of molecular interactions (enzyme reactions, protein-small
molecule, protein-protein and DNA-DNA) efficiently and sensitively.
Additionally, the magnetic variations can be figured out in turbid
media solution and in whole-cell lysates under no purification of
the protein. The advanced magnetic nano-sensors can be utilized
in different biological applications, namely homogenous assays,
reagents in miniaturized microfluidic systems, affinity ligands
for rapid and high-throughput magnetic readouts of arrays, probes
for magnetic force microscopy, and potentially for in vivo imaging.
For instance, iron oxide nanoparticles functionalized using oligonu-
cleotides aggregate in existence of target oligonucleotides, leading
to a detectable enhancement (30 ms) in the relaxation times of the
surrounding water. It was also found out that base pair insertions in
the target strand caused only increase of 2 to 5 ms in the relaxation
times, while single base pair mismatches terminated in 1–21 ms
enhancement in T2, representing that these systems could poten-
tially be employed to optionally recognize DNA mutations.
6.2. Surface modification of iron oxide nanoparticles by inorganic
materials
As described in previous sections, there have been many
considerable improvements in the generation of functionalized
iron oxide nanoparticles using organic materials. However, syn-
chronic control of shape, surface structure, biocompatibility, sta-
bility and magnetic properties of obtained nanoparticles is a great
deal. In contrast, inorganic compounds, as a reliable alternative,
can functionalize iron oxide nanoparticles, which lead to signifi-
cantly increase in the anti-oxidation properties of iron oxide
nanoparticles and consequently expand their application. In addi-
tion, functionalized iron oxide nanoparticles using inorganic
compounds are very promising candidates for extensive range of
applications including catalysis, bioseparation and biolabeling.
The main inorganic materials employed as the surface coating of
nanoparticles are different kinds of metal oxides and sulfides,
silica, metal/nonmetal etc. The functionalized iron oxide nano-
composite using inorganic materials are categorized into two
groups: first group that maintained the magnetic property of iron
oxides and the second which retained the other properties of
inorganic materials.
Through controlling the interface interactions and structure,
nanocomposites can display facile chemical and physical proper-
ties that will be crucial for upcoming technological applications.
The structure of iron oxide nanoparticles functionalized by inor-
ganic compound is divided into five shapes: shell–core, core–shell,
shella–core–shellb, mosaic, and dumbbell, in which iron oxides
were often considered as the core. Lots of studies have indicated
that in the existence of core–shell nanocomposites, like Au–Fe3O4
nanoparticles, its structure contains magnetite core and gold shell
at the outer layer. Commonly, superparamagnetic colloidal parti-
cles represent some potential in the application of biodetection
and bioseparation, It is necessary for them to be tailored at the
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
scale resembling to a virus (20–500 nm), a DNA (10–100 nm) or a
protein (5–50 nm). However, since the reactivity of iron oxide
nanoparticles strongly enhances by reduction in their dimensions,
very small particles may withstand fast biodegradation when they
are instantly subjected to biomolecules. So, matrix dispersed iron
oxide nanoparticles can be synthesized in various states and
significantly raise the iron oxide nanoparticles size. The mosaic
structure is frequently fabricated within the hollow silica spheres
with iron oxide nanoparticles, and the shell–core structure can be
built by individual iron oxides which are linked their inner layer.
Moreover, shella–core–shellb kind composite nanoparticles can be
synthesized by layer-by-layer technology and also can be domi-
nated the above restrictions. The shella may be the metal nano-
particles, quantum dots and polymer and the shellb can be similar
or different functional materials. This sort of composite nanopar-
ticles is predicted to widely extend the application area of iron
oxide nanoparticles. Dumbbell-like structure is often formed via
epitaxial growth of iron oxide (or inorganic compound nanopar-
ticles) on the inorganic compound seeds (or iron oxide nanopar-
ticles), and ultimately produced the bi-functional composite
nanoparticles.
In the following sections, the advantage arises from the possibility
of incorporating the magnetic nanoparticles with other inorganic
compounds, favoring modulation of magnetic properties of iron
oxide with unique properties of inorganic materials. This technique
can be performed either by entrapping magnetic iron oxide nano-
particles in the desired inorganic compound layers, or by connecting
magnetic iron oxide nanoparticles with the considered inorganic
materials. Several generic and recent examples will be expressed in
the discussions of each possible method and the relevant properties
and application of composite nanoparticles.
6.2.1. Metal or non-metal
Another novel technique to preserve the iron oxide nanoparti-
cles is to persuade a controlled oxidation of a pure single-metal or
nonmetal shell, including palladium, platinum, silver, gold, carbon,
iron etc. The possibility in control of the single-metal or nonmetal
layer has a massive influence on the scope of iron oxides’ applica-
tion, especially to extend its scope of biomedical and catalyst
applications. For example, gold is often applied to passivate the
surface of Fe3O4 nanoparticles to prevent oxidation. It is notable
that the silver, gold and carbon single-metal functionalization will
lead to the decrease the saturation magnetization value of the iron
oxide nanoparticles, but materials like copper, palladium, platinum
and cobalt may show opposite result, with respect to the value of
mass magnetic susceptibility for the applied materials. Further, the
dimension of iron oxide nanoparticles functionalized using metallic
or nonmetallic materials are tunable, for instance, their diameter
can be governed by adjusting the reduction and repeat times.
Generally, there are two approaches for synthesis of metal-
functionalized iron oxide nanoparticles; first one includes the direct
reduction of the ions of single-metal onto the surface of iron oxide
nanoparticles. Synthesis and coating of Fe3O4 nanoparticles using
gold and silver metals by directly reducing their ions was reported
by Mandal et al. [224]. In this way long lasting stable iron oxide
nanoparticles were successfully obtained. This technique provides
size range of 18 to 30 nm, however unlike the claims regarding to
achieving a well-defined core–shell structure, such declaration
cannot be observed from provided TEM images. Results also
presented that the saturation magnetization value of 38 emu g  1
for gold-coated iron oxide nanoparticles which is decreased about
57.6% compared to its bulk counterpart (92 emu g  1). This techni-
que frequently employs to synthesize the core–shell structure of
nanocomposite, but it tends to keep the magnetic properties of bare
iron oxides.
223
The second approach to synthesize metallic functionalized iron
oxide nanoparticles, which also very common is the reduction of
the ion of single-metal on the surface of the small molecule,
polymer or SiO2-functionalized iron oxide nanoparticles. Many
reports have been successfully prepared gold coated magnetic iron
oxide nanoparticles. Gold coatings can supply not only the stability
of the nanoparticles in the solution, but also assist in linking the
biomolecule containing –SH group into the surface of nanoparti-
cles for different biomedical applications. Wu et al. [225] have
recently used this technique to synthesize the monodispersed
gold-coated magnetite nanoparticles. They applied sonolysis tech-
nique using a suspension of gold ions and amino-modified
magnetite nanoparticles with supplementary addition of reducing
agent. The magnetic nanocomposite with diameter of 30 nm and
saturation magnetization value of 63 emu g  1 (T ¼300 K) was
obtained. It is noteworthy to mention that the resulted saturation
magnetization decreased by roughly 0.03% in comparison with the
bulk magnetite nanoparticles (65 emu g  1, T ¼10 K). Accordingly,
this technique is effective to preserve the saturation magnetization
of the naked magnetite nanoparticles. Yu et al. [226] also reported
a synthesis of bi-functional gold coated iron oxide nanoparticles
with dumbbell structure by epitaxial growth of iron oxides on the
gold seeds. The procedure includes heating of the solution of gold
nanoparticles, iron pantacarbonyl, oleic acid, 1-octadecene solvent
and oleylamine at 300 1C followed by refluxing and oxidation at
ambient condition. As a result, dumbbell-structured nanoparticles
with flexible size range of 3–14 nm were successfully obtained.
Stoeva et al. [227] reported novel synthesis of shell–core–shell
nanoparticles using shell–core SiO2–Fe3O4 nanoparticles that elec-
trostatically absorb gold-nanoparticle seeds (1–3 nm) which in a
next step play the role of nucleation sites for the growth of a gold
shell around the shell–core nanoparticles. Further functionaliza-
tion of the obtained three-layer magnetic nanoparticles was also
proposed using DNA following synthetic techniques for pure gold
nanoparticles and reversibly accumulated into macroscopic aggre-
gates using supplementary binding oligonucleotides. Moreover, Teng
et al. [228] have skillfully applied a consecutive synthetic technique
for the preparation of well-defined Pt–Fe2O3 core–shell nanoparticles
with controllable shell thickness. The obtained core–shell nanopar-
ticles could be potentially used in catalysis applications and as
precursors for making characteristic-controllable magnetic nanopar-
ticles, nanocomposites and thin films.
Considering the broad application scope of magnetic record
and magnetic ink materials lately, large number of researches have
centralized on the advancement of the coated iron oxide magnetic
nanoparticles using carbon like carbon-encapsulated magnetic
nanoparticles. Application of carbon for iron oxide coating has
the advantage of protecting role towards the iron oxide nanopar-
ticles avoiding fast degradation by environment and also nano-
particles’ agglomeration generated by van der Waals forces. Even
though coating the iron oxide using carbon leads to the reduction
of saturation magnetization of obtained product, other magnetic
characteristics slightly change. In addition, carbon-coated iron
oxide nanoparticles have many privileges among the other mate-
rials including much higher stability both chemically and ther-
mally and also biocompatibility. Newly applied techniques propose
new replacements for the controlled synthesis of facile and stable
carbon/iron oxides nanocomposites. Wang et al. [229] reported the
synthesis of carbon–magnetite nanocomposite by heating the
aqueous solution of glucose and oleic acid-stabilized magnetite
nanoparticles. Dantas et al. [230] also prepared the carbon/iron
oxides composites which can be utilized as heterogeneous cata-
lysts in the textile wastewater’s treatment procedure. Despite of
tremendous beneficial characteristic of carbon-functionalized iron
oxide, the synthesis of monodispersed iron oxide nanocomposite
in isolated from is still great challenge need to be overcome.
224 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
Additionally, iron oxide nanoparticles functionalized using single-
metal (particularly noble metal) also applied as catalysts like
Au–Fe2O3 catalyst for oxidation of CO [231,232], Au–α-Fe2O3 catalyst
for water–gas shift reaction [233,234], Pd-Fe3O4nanoparticle-based
catalyst for the cross coupling of acrylic acid with iodobenzene [235]
and decarboxylative coupling reaction in aqueous media [236], Ag-
Fe3O4 catalyst for epoxidation of styrene [237], etc. These matrix-
structured heterogeneous catalysts are regularly improved as the
magnetically recyclable catalysts (MRCs) in the last years and can be
much helpful to cooperate an effectual separation and recovery in a
liquid-phase reaction by a magnet, particularly when the catalysts
have the nano-scaled and own higher activities compared to their
pure and bulk single-metal or nonmetal [238,239]. Consequently, the
advancement of the novel and fast techniques for the synthesis of
efficient MRCs is a big deal.
Therefore, many attempts have been made for obtaining the
nano-scaled magnetically recyclable catalysts possessing easy
separation characteristics and high activity. To give an example,
Lin and Chen [240] reported a synthesis of gold-coated iron oxide
catalyst with high CO oxidation activities under low temperature
prepared by deposition–precipitation technique. In this study, the
MRC’s size and specific surface area can be controlled by adjusting
the pH value within the experimental procedure and the calcina-
tion temperature. Furthermore, after 90 min time on stream, the
CO conversion can be fully approached. A similar study was done
by Avgouropoulos et al. [241] indicates that the gold-hematite
catalyst is premier to the CuO–CeO2 and Pt/γ-Al2O3 for the CO
oxidation at rather low temperatures (80–120 1C).
6.2.2. Metal oxides/sulfides
A large number of researches have been concentrated on
the functionalization of iron oxide nanoparticles using the metal
oxides and sulfides, basically due to their exclusive physico-
chemical properties which can be imported to the bare iron oxide.
Initially a wide range of studies has devoted to applying much more
common materials such as Al2O3, SnO2, CaO, MgO, ZnO and
etc. [242–245], optical and electrical materials like TiO2, ZnS etc.
[245–247] and magnetic materials including iron oxides, CoFe2O4,
NiO and CoO [248]. Li et al. [249] successfully synthesized magne-
tite–aluminium oxide core–shell nanoparticles using a chemical
alternative procedure indicating high stability in the air. The
relatively uniform nanoparticles are claimed that along with cap-
tured phosphopeptides can be directly deposited on the matrix-
assisted laser desorption/ionization target for analysis due to its
high magnetic response. In another study performed by Hong et al.
[250], synthesis of ZnO-coated Fe3O4 core–shell nanoparticles was
reported in which the coating were processed by direct precipita-
tion of zinc acetate and ammonium carbonate on the magnetite
nanoparticles. The results showed that the anti-oxidation capability
of the functionalized nanoparticles surpasses that of the bare
magnetite nanoparticles. Nevertheless, the obtained particles did
not fulfill high uniformity as well as saturation magnetization which
decreased from 67.78 to 20.33 emu g  1.
In the case of magnetic materials coating, the functionalized
iron oxide nanoparticles normally show a significant effect
towards the magnetic properties. The association of two different
magnetic phases provides novel functionalized iron oxide nano-
particles, having lots of feasible applications. Fabrication of well-
defined magnetite-cobalt ferrite nanoparticles was reported by
Cheon et al. [251,252]. The preparation procedure shows a specific
ferrimagnetic phase transformation behavior by nanometer size
redox chemical reactions resulting in the considerable enhance-
ment of the saturation magnetization value and coercivity.
Moreover, optical and electrical potentially materials can be used
to functionalize iron oxide nanoparticles which definitely develop
the applied fields of the iron oxide nanoparticles. Wang et al.
reported the superparamagnetic maghemite Cadmium selenide-
zinc sulfide quantum dots nanoparticles possessing both magnetic
and luminescent properties. The obtained average size of this
nanocomposite was estimated roughly 20 nm, it also displayed
quantum efficiency and was simply able to be distinguished from
solution using permanent magnet. The resulted nanoparticles were
applied in cell separation; further they can be utilized in various bio-
analytical experiments encompassing either luminescence detection
or magnetic separation [253]. Lately, Li et al. described a preparation
of magnetite–titanium dioxide nanocomposite using a triple-step
procedure. Primarily, Fe3O4 nanoparticles were prepared through
solvothermal technique applying FeCl3 as the iron source along with
ethylene glycol play simultaneous role of solvent and reducing agent.
Then, Fe3O4 nanoparticles were coated within a thin layer of carbon
by the hydrothermally polymerization and carbonization of glucose
as precursor. Ultimately, the pre-hydrolyzed tetrabutyl titanate was
attracted onto the surface of nanocomposite and transformed into
TiO2 through calcination treatments under nitrogen. The mentioned
nanocomposite can be applied for optional development of phospho-
peptides simply in phosphoproteome analysis as it owns the magnetic
properties [254]. Chen et al. [255] have also fabricated the functional
magnetite–titania core/shell nanoparticles can be employed as photo-
killing agents for pathogenic bacteria. In conclusion, a large number of
optical and electrical materials used to functionalize iron oxide
nanoparticles exhibiting potential application in the biological
technology.
6.3. Effects of surfactants on electrochemical synthesis of iron oxide
nanoparticles
Surfactants are used as director agents to control the mechan-
ism and kinetics of the reactions in synthesis processes of
nanomaterials. These additives can affect the morphology and
particles sizes of the final product [256]. The sizes distribution of
the nanoparticles can be controlled by adding a surfactant [257].
Cabrera et al. [157] applied amine as surfactant to synthesize
Fe3O4 nanoparticles in the range of 20 to 30 nm. The role of amine
during the synthesis has been reported as capping and supporting
agent to control the size and aggregation of the particles. Size
controlling would come through by adjusting the key parameters of
the electrochemical synthesis such as current density and potential.
Yuan et al. [258] reported synthesis of mesoporous crystalline
akaganeite using cationic, anionic and nonanionic surfactants by
electrochemical method. They claimed that the surfactant presence
in the reaction medium would lead to enhance the required pH for
akaganeite formation along with decreasing the particle size of
akaganeite to the nano range. Moreover, it is believed that surfac-
tants play an important role in the hierarchical nanoparticles
assembly and scaffold-like structure of akaganeite particles by
preliminary mediation of their size and intergrowth. Eventually,
they assisted to develop the formation of akaganeite through
rearranging their growth and aggregation by the formation of
hydrogen bonds with surface O–H groups.
Maliar et al. [133] prepared iron particles by reduction of FeSO4
electrochemically using reducing agents. They reported that surfac-
tants were one of the key parameters which changed the rate of
anodic/cathodic reactions followed by shifting of the open circuit
potential (OCP). Addition of surfactant could alter the OCP values of
iron electrodes, particularly the rate of potential shift at the starting
point. Moreover, polarization values were also increased because of
adsorption of surfactants. In terms of particle formation, the presence
of surfactant in the medium of reaction led to the formation of a
protective shell surrounding of iron particles that avoids the particles
from agglomeration. Therefore, surfactants existence resulted in
decreasing the particle size down to nano-scale in water-phase.
 D. Ramimoghadam et al. / Journal of Magnetism and Magnetic Materials 368 (2014) 207–229
In the case of synthesis of iron particles in the oil-phase, surfactant
molecules can adsorb both on Fe/oil and micelle/oil interfaces which
facilitate the coalescention of released iron particles and micelles. Both
these factors increase the rate of forming and size of resulting iron
particles under the electrochemical mechanism.
7. Conclusions and future prospects
Iron oxide nanoparticles are receiving much attention due to
their extensive applications in various fields of chemical indus-
tries, medicine, magnetic storage, biomedical devices and waste-
water treatments. The synthetic methodologies of nanoparticles
are typically including co-precipitation, hydrothermal, sol–gel,
microemulsion, sonochemical, dry vapor deposition, surfactant
mediation etc. are used to obtain different iron oxide phases. All
these synthetic methods have several cons and pros for iron oxide
nanoparticles preparation. Although mentioned methods above
often lead to relatively narrow size distributions, they are prone to
optimize for favorite particle size, morphology and surface func-
tional groups. In the case of controlling the morphology and size of
the iron oxide nanoparticles, hydrothermal method along with
thermal decomposition are considered the ideal methods. To
obtain the biocompatible iron oxide nanoparticles possessing
water solubility, co-precipitation technique is frequently applied,
however, this method lacks in the shape and morphology control-
ling, often results in broad size distributions and particle aggrega-
tion. As a time competitive replacement, sonochemical route can
be employed to synthesize iron oxide nanoparticles with extra-
ordinary magnetic properties.
Among all synthetic methods, prospects for electrochemical
synthesis of iron oxide nanoparticles seem very promising, since
electrochemical synthesis is
 A convenient, environmentally-friendly, selective and cost-
effective technique.
 Electrodes give rise to chemical changes in the absence of toxic
reagents.
 Normally at experiments runs at low temperatures or at
ambient conditions.
 Reactions reduce the local consumption of energy, the risk of
corrosion, material failure, and accidental release.
 Also, reactions may occur in low volatility or no-volatility reaction
media.
 The electrodes may be regarded as heterogeneous catalysts that
easily separate from the products.
 It is briefly straightforward, reproducible, pure, time saving
and inexpensive method to synthesize magnetic iron oxide
nanoparticles.
However, electrochemical synthesis of iron oxide nanoparticles
is being poorly studied. Indeed, some challenges need to be dealt
to fulfill novel efficient and unique iron oxide nanoparticles. In
electrochemical synthesis, factors such as current density, pH,
electrolyte concentration, electrode choice etc., play important
role in the reaction. Future studies shall aim to address the effect
of these parameters on size, morphology, shape and magnetic
properties of iron oxide nanoparticles.
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