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Tuning the properties of cobalt ferrite: a road

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towards diverse applications

Cite this: RSC Adv., 2016, 6, 97694
Sheenu Jauhar, Japinder Kaur, Ankita Goyal and Sonal Singhal*

Received 23rd August 2016
Accepted 5th October 2016
DOI: 10.1039/c6ra21224g
www.rsc.org/advances
Cobalt ferrite has gained great scientic interest because of its unique properties and exceptionally
promising applications. A large number of synthetic methods, such as solgel auto-combustion method,
co-precipitation method, ball milling method, microemulsion method, polyol method, etc. have been
used for its synthesis. Synthetic methodologies and heat treatment given to the sample strongly
inuence the particle size of the synthesized ferrite, which in turn determines its properties. In addition,
the properties of cobalt ferrite can be altered by dierent chemical modications such as substituting
one or more ions from the lattice with some other metal ion, modifying the reaction conditions,
compositing with dierent inorganic matrices etc. The most prominent inuence on the properties of
ferrites is exerted by variation in cation distribution. Among all the factors the major inuence on the
cation distribution is laid by doping. Guest metal ions according to their site preference occupy dierent
lattice sites, thereby, changing the structural, magnetic, electrical and the catalytic properties of cobalt
ferrite. In this review, we summarize the signicant developments involving modications in synthesis
and properties of cobalt ferrite. This review also highlights the advances in the applications of cobalt
ferrite in the elds of catalysis, biomedicine and sensors.

hydrogen production, multi-layer chip inductors, high density

1. Introduction
In the past century, spinel ferrites have emerged as forefront
materials in the eld of material synthesis and engineering.
This is largely attributed to the ease with which their properties
can be tuned as well as their vast applications. Some of their
traditional applications include transformer applications, solar
Department of Chemistry, Panjab University, Chandigarh, 160014, India. E-mail:
sonal1174@gmail.com; sonal@pu.ac.in; Fax: +91-172-2545074; Tel: +91-172-
2534421; +91-9872118810
magnetic recording, telecommunications, microwave devices,
as contrast agents in magnetic resonance imaging (MRI),
sensors, catalysts etc.110 However, in recent years, many new
avenues have opened and the latest research on spinel ferrites
has developed in innumerable directions, increasing their
potential applications to a much greater extent.
Among various types of spinel ferrites, cobalt ferrite,
CoFe2O4, is of utmost importance. It has an inverse spinel
structure which can be represented by the formula
(CoxFe1
x)A[Co1
xFe1+x]BO4. The value of x depends on various

Dr Sheenu Jauhar received her Dr Japinder Kaur obtained her

MSc. (Hons School) degree Ph.D. degree in Chemistry in
(2007) in chemistry from the 2016 from Department of
Department of Chemistry and Chemistry and Centre of
Centre of Advanced Studies in Advanced Studies in Chemistry,
Chemistry, Panjab University, Panjab University, Chandigarh.
Chandigarh (India). She She is currently working as
completed her Ph.D. degree in Research Associate at Bhabha
2014 under the title-so ferrites Atomic Research Centre, Trom-
and the study of their structural, bay. Dr Japinder Kaur has pub-
magnetic, electrical, optical and lished 10 papers in international
catalytic properties. reputed journals and more than
20 papers were presented in
national and international conferences. Her research eld includes
synthesis of nanostructures and their application as photocatalyst.

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factors such as method of preparation, preparation conditions,
thermal treatment, etc. It has a high coercivity, moderate satu-
ration magnetization and a high Curie temperature.11,12 It has
excellent chemical stability, good mechanical hardness and
good electrical insulation. It is a hard magnetic material and its
magnetic properties exhibit size dependence.
In addition, the spinel structure of cobalt ferrite allows the
introduction of dierent metallic ions into its lattice, thus
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altering the structural, magnetic, electrical and catalytic prop-
erties. The distribution of cations over the tetrahedral and
octahedral sites depends on various factors like size of the
substituent ion, charge possessed by the substituent ion, site
preference of the substituent ion, methodology adopted for the
synthesis, preparation conditions and the extent of substitu-
tion. A large volume of work is reported on the modication of
dierent properties of cobalt ferrite via adopting dierent
methodologies, reaction conditions and substitution of
dierent metal ions. The major purpose of this review is to
summarize the vast and benecial knowledge regarding the
synthesis, properties, applications and possible modications
of cobalt ferrite in a concise and eective way.
It is well established that the properties of cobalt ferrite
nanoparticles are dependent upon the method of synthesis and
the reaction conditions. Therefore, it is essential to throw some
light on the method of synthesis of cobalt ferrite and their
inuence on the properties of nal product.
2. Synthetic methods and their
inuence on properties of cobalt ferrite
Cobalt ferrite can be synthesized by various synthetic methods
like ceramic method,13 solid state reaction technique,14
co-precipitation method,1522 solgel auto-combustion method,2327
microemulsion processing,28 polyol method,2931 solvothermal
method,3236 electrochemical synthesis,37,38 and ball milling
Ankita Goyal received her MSc.
(Hons School) degree in Chem-
istry (2012) from the Depart-
ment of Chemistry and Centre of
Advanced Studies in Chemistry,
Panjab University, Chandigarh
(India). Currently, she is
pursuing her Ph.D. in Dr Sonal
Singhal's group. Her current
research work includes the
benecial structural modica-
tions in the magnetically
retrievable ferrite nano-
structures for catalytic
applications.
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method.39 These synthetic methodologies for the fabrication of
cobalt ferrite nanoparticles are briey discussed below:
2.1. Ceramic method
In this methodology metal oxides are generally used as
precursors and very high temperatures are required. Metal
oxides in stoichiometric amounts are taken, homogenized and
pre-annealed at very high temperature and then cooled, fol-
lowed by second annealing at high temperature for several
hours so to obtain ferrites. Murugesan et al.13 synthesized cobalt
ferrite nanoparticles using both solgel methodology and
ceramic technique and compared the properties of both the
samples. It was found that the value of lattice constant and
saturation magnetization was higher for the ceramic synthe-
sized method while coercivity was less.
2.2. Solid state reaction technique
Similar to ceramic processing, in solid state reaction technique
the precursor metal oxides are mixed together and ground in
a pestle mortar and annealed at high temperatures followed by
grounding in pestle mortar to ensure homogenization of the
precursors. Aerwards, second annealing is performed to
obtain ferrite powders. Pandit et al.14 synthesized cobalt ferrite
nanoparticles employing solid state reaction technique and
observed the saturation magnetization of 57.0 emu g
1 and
coercivity of 590 Oe.
Both the ceramic method and solid state reaction technique
suer from uncontrolled stoichiometry, poor composition,
chemical inhomogeneity, contamination, coarser particle size,
and introduction of impurities during grinding and high
annealing temperature. In this context, wet chemical methods
have emerged as saviour and oer ferrite nanoparticles with
reproducible stoichiometric composition and desired micro-
structures. Due to these reasons wet-chemical routes have
garnered immense importance of researchers.
Dr Sonal Singhal, Associate
Professor, Department of Chem-
istry and Centre of Advanced
Studies in Chemistry at Panjab
University, Chandigarh, India.
She obtained her Ph.D. degrees
in Chemistry in 2003 from IIT
Roorkee, India. She joined
Department of Chemistry, Pan-
jab University as Assistant
Professor in the year of 2005. Dr
Singhal has more than 10 years
of teaching experience, and has
published 85 papers in the international reputed journal and
more than 50 papers were presented in the national and interna-
tional conferences/symposia. Her research interests include:
synthesis, characterization and applications of various types of
nano materials of ferrites and their composites.
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2.3. Co-precipitation method
Co-precipitation method is a facile and clean wet-chemical
methodology for the fabrication of cobalt ferrite magnetic
nanoparticles. This method oers good control of shape and
size distribution and good chemical homogeneity. In this
methodology, metal salts are taken in stoichiometric amounts
and are dissolved in desired solvent followed by the addition of
a precipitating agent, such as, NaOH, liquor ammonia, etc. to
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obtain desired pH. Then the sample is subjected to heat treat-
ment for the growth and crystallinity of particles.
Gul et al.15 synthesized cobalt ferrite nanoparticles via
co-precipitation method using metal nitrates as precursors and
NaOH as precipitating, at pH 1212.5. The obtained samples
were annealed at 800  C for 6 h. The authors reported that the
synthesized ferrite has a crystallite size of 17 nm and a lattice
constant equal to 8.378 A with saturation magnetization of
61.5 emu g
1 and coercivity of 509 Oe.
El-Okr et al.16 employed metal chlorides as precursors,
NH4OH as precipitating agent and the synthesis reaction was
carried out at dierent temperatures of 20, 40, 60, 80  C. The
authors observed that samples synthesized at 20 and 40  C
exhibit an amorphous character. Contrary to this, samples
synthesized at 60 and 80  C displayed crystalline nature. Further
the eect of annealing temperature was also studied and it was
observed that increase in annealing temperature results in
increase in lattice parameter, crystallite size and saturation
magnetization. Similar studies were carried out by Sartoratto
et al.17 who annealed cobalt ferrite prepared by co-precipitation
method from 100  C to 1200  C for 1 h and concluded that the
crystallite size increased with increase in annealing tempera-
ture and the lattice parameter of cobalt ferrite annealed at
1200  C was 8.396 A, which corresponded to the lattice
parameter of the bulk sample. Similar eect of annealing
temperature on the lattice parameter, crystallite size and satu-
ration magnetization was observed by Zhang et al.18
2.4. Solgel auto-combustion method
Solgel auto-combustion method is another extensively used
wet-chemical method for the synthesis of cobalt ferrite. This is
a rapid and inexpensive process and yields highly pure and
crystalline nano materials with homogeneous size distribution.
This is a liquid phase process involving hydrolysis and
condensation, in which stoichiometric amounts of metal
precursors are dissolved in minimum amount of distilled water
followed by the addition of a chelating agent like citric acid,
ethylene glycol, glycine etc. The pH of resultant solution is then
adjusted by adding dilute ammonia solution. Then the solution
is allowed to evaporate till gels are formed, which on contin-
uous heating undergo combustion to give a solid powder. This
solid powder is annealed in a furnace at various temperatures.
Ai and Jiang23 mixed metal nitrate solutions taken in stoi-
chiometric amounts with citric acid solution followed by the pH
adjustment to 7. The obtained mixture was reuxed at 100  C
for 2 h to form metal citrate complex followed by rising the
temperature. The authors observed that the values of saturation
magnetization and coercivity of as obtained samples were lower
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than the values for bulk ferrite. However, an initial increase in
the value of coercivity with increase in the annealing tempera-
ture followed by decrease in coercivity was observed. On the
other hand, there was continuous increase in the values of
saturation magnetization and particle size. Cannas et al.24
synthesized a series of cobalt ferrite nanoparticles dispersed in
a silica amorphous matrix using solgel method. It was
observed that samples with small amount of cobalt ferrite (5, 10
and 15 wt%) are spherical with narrow particle size distribution,
while the samples with high cobalt ferrite content (30 and 50
wt%) were observed.
Sajjia et al.25 synthesized a series of cobalt ferrite nano-
particles using dierent crosslinkers and complexing agents at
dierent temperature conditions. It was found that complexing
agent and cross linkers had a crucial eect on the particle size
and size distribution of the particles.
2.5. Microemulsion processing
A microemulsion is dened as a thermodynamically stable
isotropic dispersion of two relatively immiscible liquids, con-
sisting of microdomains of one or both liquids stabilized by an
interfacial lm of surface active molecules. These may be clas-
sied as water-in-oil type microemulsion or oil-in-water type
microemulsion depending on dispersed and continuous pha-
ses. These have a dynamic structure in which the droplets of the
dispersed phase are colliding with each other. Such collisions
are inelastic and lead to coalescence of droplets, due to which
droplets temporarily merge with each other. However, aer
sometime, these droplets break to form separate droplets. The
size and the shape of the particles formed depend on the size
and the shape of the droplet. The coagulation of the particles of
the precipitate is hindered by the surfactant.
Pillai and Shah28 synthesized cobalt ferrite nanoparticles
using water/CTAB/n-butanol/octane microemulsion and
annealed the obtained powder at 600  C for 5 h. The saturation
magnetization of cobalt ferrite synthesized by this method was
65 emu g
1 and remanence was 29 emu g
1. However, the
cobalt ferrite particles synthesized using this method had
a high coercivity of 1440 Oe. This was attributed to the fact that
the droplets of the microemulsion restricted the particle
growth, due to which the particles formed were single-domain,
giving rise to high coercivity.
2.6. Polyol method
Another method which is employed for the ferrite synthesis is
the polyol method. In this method, a high boiling solvent, such
as ethylene glycol is used, which acts both as a solvent and
reducing agent of the metallic ions under reux conditions.
Ibrahim et al.29 synthesized cobalt ferrite by this method and
annealed the ferrite powder at 600  C and 800  C for 3 h. The
authors reported that the saturation magnetization increased
from 27.76 emu g
1 to 51.46 emu g
1 when the annealing
temperature was increased from 600  C to 800  C. The satura-
tion magnetization values of cobalt ferrite synthesized using
polyol method are, comparatively, lower than those synthesized
using co-precipitation method.
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2.7. Solvothermal method
Solvothermal technique refers to any homogeneous chemical
reaction in the presence of a particular solvent above the room
temperature and at pressure greater than 1 atm in a closed
system.40 When the solvent used is water then the methodology
is named as hydrothermal. The parameters which inuence the
properties of resultant ferrite are pH of the solution, tempera-
ture and duration of synthesis. The reaction is carried out in
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a sealed steel vessel, called as autoclave, which can withstand
high temperature and pressure for long time. A major advan-
tage of hydrothermal reaction is that high processing temper-
ature is not needed.
Zhao et al.32 synthesized cobalt ferrite nanoparticles via
hydrothermal process using CTAB as surfactant. Under
controlled reaction conditions, single domain critical size of
70 nm was obtained with high coercive force (4.6 kOe) and high
squareness ratio (0.65). Similarly, single crystalline cobalt
ferrite nanorods were fabricated by Ji et al.33 using CTAB as
surfactant via hydrothermal route. The diameter of nanorods
was found to be 25 nm with length upto 120 nm. The authors
also discussed the formation mechanism of cobalt ferrite.
The temperature dependent magnetic properties of cobalt
ferrite synthesized by hydrothermal method were investigated
by Zhang et al.34 The average crystallite size of nanoparticles was
found to be 7.6 nm. Above 380 K, superparamagnetism was
observed, which was attributed to ip of spins. However, below
20 K, a frozen spin-glass like state was found, which was
accompanied with the decrease in coercivity and enhancement
of saturation magnetization. Cobalt ferrite nanocrystals having
high saturation magnetization and coercivity were prepared via
hydrothermal method by Goh et al.35 The authors also reported
that the shape of cobalt ferrite nano-crystals changed from
spherical to rod shaped on changing the hydrothermal
temperature.
2.8. Electrochemical synthesis
Electrochemical synthesis refers to the synthesis of any material
in an electrochemical cell. This is a very ecient and economic
method for synthesizing highly pure nanomaterials at low
synthetic temperatures. Mazario et al.37 synthesized cobalt
ferrite nanoparticles using electrochemical synthesis at
dierent temperatures between 25  C and 80  C. The diameter
of nanoparticles was found to increase from 21 nm to 40 nm
with increase in reaction temperature form 25  C to 80  C.
However, the sample prepared at 60  C had highest saturation
magnetization of 80 emu g
1 at room temperature and 110 emu
g
1 at 5 K.
2.9. Ball milling method
In certain applications, such as non-contact stress sensors and
actuators, magnetostrictive materials are considered suitable.
Magnetostriction is dened as that property of a material which
causes it to change its shape or dimensions when a magnetizing
eld is applied onto it. In order to produce such materials, ball
milling method is considered suitable. The method involves the
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ball milling of ferrite particles in ball milling apparatus. The
powders so obtained are then pressed into buttons and sintered
at dierent temperatures. The magnetostriction of the ferrites
synthesized by this method is dierent at dierent annealing
temperatures and is found to be larger at lower sintering
temperatures. Nlebedim et al.39 synthesized ball milled cobalt
ferrite nanoparticles at dierent vacuum sintering tempera-
tures and times. The authors observed the formation of
secondary phase Co1
xFexO4 (x  0.33), which resulted into
decrease in magnetostriction. Moreover, sintering temperature
was found to greatly inuence the magnetostriction. The lowest
anisotropy was found for the samples sintered at higher
temperatures and longer times.
Similarly, Moyet et al.41 studied the magnetic properties of
high energy ball-milled bulk cobalt ferrite material. The authors
concluded that 1 h of ball milling drastically changed the
crystallite size. The authors also reported enhancement in the
values of coercivity, which was attributed to the presence of
defects in the crystal structure. The saturation magnetization
values were reported to decrease with increase in milling time.
From the above discussed literature, it is evident that the
method of preparation strongly inuences the particle size and
the properties of ferrite nanoparticles. Another parameter
which strongly determines the properties of cobalt ferrite is the
substitution of dierent metal ions into its lattice. Thus, it is
necessary to understand the changes brought about by substi-
tution of dierent ions into the cobalt ferrite lattice.
2.10. Thermal decomposition methodology
Thermal decomposition method is an important methodology
for the synthesis of ferrites with a uniform and narrow size
distribution at a large scale. In this methodology the idea of
seed-mediated growth is used for the production of high-quality
and monodisperse ferrite nanoparticles. Also shape and size of
the nanocrystals can be well controlled by the choice of
precursors and by controlling the growth rate. Hyeon et al.42
synthesized highly crystalline and monodisperse cobalt ferrite
nanocrystals by the high-temperature aging of a metalsurfac-
tant complex followed by mild oxidation. Particle sizes were
varied from 4 to 9 nm by changing the experimental conditions.
Nanocrystal sizes could be controlled by changing the molar
ratio of stabilizing agent to precursor and also by using dierent
stabilizing agents such as oleic acid, lauric acid etc.
Song and Zhang43 carried out the shape controlled synthesis
of highly magnetic cobalt ferrite nanocrystals and studied the
eect of shape and size on the magnetic properties. The authors
established that the shape of the nanocrystals can also be
reversibly interchanged between spherical and cubic morphology
through controlling nanocrystal growth rate. Furthermore, the
magnetic studies show that the blocking temperature, satura-
tion, and remanent magnetization of nanocrystals are solely
determined by the size regardless the spherical or cubic shape.
However, the shape of the nanocrystals is a dominating factor for
the coercivity of nanocrystals due to the eect of surface anisot-
ropy. On the similar basis, Baaziz et al.44 synthesized spherical
coreshell CoxFe1
xO@CoyFe3
yO4 nanoparticles as well as
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spherical and cubic shaped CoFe2O4 were synthesized through
a thermal decomposition method by the variation in the nature
of precursors and ligands. The shape and arrangement of the
particles was found to directly aect the magnetic characteristics
of the samples. The properties of CoFe2O4 specially, the magnetic
characteristics synthesized by thermal decomposition method
with dierent variations in the precursors or the adopted meth-
odology have been evaluated many authors.4547
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3. Inuence of type of substituent
ions on properties of cobalt ferrite
Cobalt ferrite has an excellent ability to incorporate various
metal ions into its lattice. In turn, the metal ions inuence the
properties of cobalt ferrite to yield materials with new and
interesting properties. The properties of substituted cobalt
ferrite depend on the type of metal incorporated, the site pref-
erence energy for that metal and the cation distribution of the
ferrite. The inuence of various metal ions on the properties of
cobalt ferrite is discussed ahead.
3.1. Substitution with representative elements
Representative elements are the elements which belong to the s-
and the p-block. These constitute groups 12 and groups 1318
of the periodic table. As compared to the transition metal
substituted cobalt ferrites, little literature is available on these
elements as substituents. This may be attributed to the reason
that various representative elements do not prefer to crystallize
in a spinel lattice. For instance, lithium forms a ferrite having
formula LiFe5O8. Similarly barium and strontium form hexag-
onal ferrites like BaFe12O19 and SrFe12O19.
Dlamini et al.48 synthesized MgxCo1
xFe2O4 (0 # x # 1.0)
nanoferrites and observed a strong dependence of the magnetic
properties and crystallite size on Mg2+ concentration. The
authors observed a decrease in crystallite size and increase in
coercivity with increase in Mg2+ content. Bouhas et al.49
synthesized calcium substituted cobalt ferrites CayCo1
yFe2O4,
y 0.00, 0.05 and 0.10. It was proposed that the calcium ions
preferred to occupy tetrahedral A-sites of the ferrite sub-lattice.
Singhal et al.50 synthesized aluminum substituted cobalt
ferrites, CoFe2
xAlxO4 (x 0.0, 0.2, 0.4, 0.6, 0.8, 1.0, 1.2 and 1.4).
There was a linear decrease in lattice parameter and saturation
magnetization with increase in Al3+ concentration. Similarly,
Aghav et al.51 prepared CoAlxFe2
xO4 (x 0.0, 0.2, 0.4, 0.6, 0.8
and 1.0) and observed similar behavior for saturation magne-
tization. With the introduction of Sn, Ga and Bi in to the lattice
of cobalt ferrite, an increase in lattice parameter was observed
due to bigger size of guest metal ions.5254 Also the saturation
magnetization decreased with Sn and increased with Bi and Ga
due to non-magnetic character of Sn.
3.2. Substitution with transition elements of rst transition
series
Cobalt ferrites substituted with 3d-transition elements are the
most widely studied among substituted cobalt ferrites owing to
the facile incorporation of these ions into the lattice of cobalt
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ferrite due to the comparable sizes of the host and the guest
ions. Vast literature is available for transition metal substituted
cobalt ferrites.
Scandium substituted cobalt ferrites CoScxFe2
xO4 (0.0 # x
# 1.0) were synthesized by Lefevre et al.55 With increasing
concentration of scandium ions, the lattice parameter and curie
temperature increased and crystallite size decreased. Rao et al.56
synthesized CoFe2
xTixO4 (0.00 # x # 0.30) and observed that
with increase in Ti4+ concentration, the lattice parameter
increased and saturation magnetization decreased due to the
octahedral site preference of Ti4+ ions. The d.c. resistivity of the
ferrite samples increased with Ti4+ concentration due to
expansion of lattice. The inuence of chromium addition on the
properties of nano-crystalline cobalt ferrite system has been
studied by various researchers.5762 Koseoglu et al.57 synthesized
chromium substituted cobalt ferrite (CoCr0.3Fe1.7O4). The
lattice parameter of chromium substituted cobalt ferrite was
smaller than that of pure cobalt ferrite due to smaller size of
Cr3+ as compared to Fe3+ ions. Also saturation magnetization
decreased due to octahedral site preference of Cr3+. Similar
trend in the lattice parameter and saturation magnetization was
observed by Iqbal and Siddiquah58 who synthesized CoCrx-
Fe2
xO4 (x 0.0 to 1.0). However, the d.c. resistivity increased
with increase in Cr3+ concentration, which was attributed to the
dilution of electron hopping between Fe2+Fe3+ ions caused by
the existence of Cr3+ ion in a stable oxidation state of +3. Han-
kare et al.59 studied the catalytic activity of CoCrxFe2
xO4 (x
0.0, 0.5, 1.0, 1.5 and 2.0) ferrites towards the acetylation of
phenols. The mechanism of acetylation and benzoylation of
phenols in the presence of ferrite catalysts is shown in Scheme
1. The authors observed that pure cobalt ferrite had better
catalytic activity as compared to chromium substituted cobalt
ferrite. Singhal et al.60 also synthesized CoCrxFe2
xO4 (x 0.0,
0.2, 0.4, 0.6, 0.8 and 1.0) and observed a decrease in saturation
magnetization from 77.0 emu g
1 to 13 emu g
1 with the
increase in Cr3+ ion concentration. This suggested the occu-
pancy of Cr3+ ions into the octahedral sites of the ferrite sub-
lattice.
Manganese doped cobalt ferrites are promising materials for
magnetic stress sensors, non-contact torque sensing, magne-
tomechanical and high magnetostriction applications.63
Various authors have synthesized manganese doped cobalt
ferrites and have reported dierent oxidation states for
manganese ion. Koseoglu et al.64 synthesized manganese doped
cobalt ferrites MnxCo1
xFe2O4 (x 0.0, 0.2, 0.4, 0.6, 0.8 and
1.0). The lattice parameter decreased while saturation magne-
tization increased with increase in Mn2+ concentration. This
behavior was attributed to the smaller size of Mn2+ as compared
to Co2+ and substitution of Co2+ ions (magnetic moment 3 mB)
by Mn2+ ions (magnetic moment 5 mB) at the octahedral sites
of the ferrite sub-lattice respectively. A similar increase in
saturation magnetization with increase in amount of Mn2+ ions
in cobalt ferrite was observed by Vlazan et al.65 Caltun et al.66
synthesized CoMnxFe2
xO4 (0.0 # x # 0.6) and reported that the
saturation magnetization decreased with increase in manga-
nese concentration due to replacement of Fe ions with that of
Mn.
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Scheme 1 Plausible reaction mechanism of acylation and benzoylation of phenols (this gure has been adapted/reproduced from ref. 59 with
permission from Elsevier).
On the similar basis, CoMnxFe2
xO4 (x 0.2, 0.4, 0.6, 0.8 and
1.0) were synthesized by Jauhar et al.67 and the saturation
magnetization values were observed to decrease with increasing
manganese concentration. Additionally, the catalytic properties
for H2O2 assisted degradation of cationic and anionic dyes were
studied. Over 90% of dye degradation was achieved in a time
period of 40 to 90 min in dark and within 20 to 30 min under
visible light irradiation. In all the reactions, it was observed that
the presence of Mn3+ ions in the cobalt ferrite lattice signi-
cantly augmented the degradation of dyes. Further, an increase
in dye degradation was observed with increase in manganese
content. It was proposed that the presence of Mn3+ ions at the
catalytically active octahedral sites was responsible for the
increased catalytic activity of ferrite compositions. Yadav et al.68
synthesized Co1
xMnxFe2O4 (0.0 to 0.5) and observed that
introduction of manganese ions inuenced the morphology of
the ferrite compositions. Interestingly for x 0.1, 0.2 and 0.3,
a uniform microstructure was obtained. However, on further
increase in x, there was enhancement in intergranular pores.
The morphology of the various manganese substituted ferrite
compositions is shown in the SEM images given in Fig. 1. The
structural and magnetic properties of cobaltmanganese
ferrites were also studied by Kambale et al.69 The magnetic
measurements indicated that the coercivity of the samples
increased with increasing manganese content and the sample
Co0.7Mn0.3Fe2O4 exhibited superior magnetic properties. Goyal
and co-workers70,71 fabricated manganese substituted cobalt
ferrite nanoparticles and carried out the reduction of nitro-
aromatic compounds. Authors found pure cobalt ferrite to be
inactive for the same. But upon introduction of Mn3+ ions into
cobalt ferrite lattice, there was dramatic increase in catalytic
eciency. Amongst dierent catalysts, CoMn0.2Fe1.8O4 was
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found to be best catalyst for the reduction reaction, which could
be attributed to the highest Fe3+/Mn3+ and Co3+/Mn3+ ionic ratio
at the catalytically active octahedral sites.
In recent years, nickel substituted cobalt ferrites have gained
tremendous importance due to their unique properties. These
have potential applications in ferrouid technology and can be
used as microwave absorber and electromagnetic shielding
materials. Due to these applications, the properties of nickel
substituted cobalt ferrites have been widely investigated.7280
Sontu et al.72 synthesized Co1
xNixFe2O4, x 0, 0.25, 0.5, 0.75
and 1.0 and observed that variation in Ni2+ content does not
aect the average crystallite size of ferrite samples and sizes fall
in a small range (3850 nm). However, the lattice parameter
decreased from 8.416 A to 8.347 A. Similarly saturation
magnetization decreased from 60.5 to 25 emu g
1 with increase
in Ni2+ content. Thus, authors commented that substitution of
nickel into cobalt ferrite lattice can tune the magnetic proper-
ties of the ferrite material from the hard magnetic and lower
resistivity cobalt ferrite to so magnetic and high resistivity
nickel ferrites.
Maaz et al.73 also studied the magnetic properties of Nix-
Co1
xFe2O4 (0 # x # 1). Both coercivity and saturation
magnetization decreased with increasing Ni2+ concentration.
The authors attributed the decrease in coercivity to the lower
magnetocrystalline anisotropy of Ni2+ as compared to Co2+ ions.
The decrease in the saturation magnetization was attributed to
the lower magnetic moment of Ni2+ ions as compared to Co2+
ions and their occupancy in the octahedral sites of the ferrite
sub-lattice. Similar trends in the lattice parameter and satura-
tion magnetization with increase in nickel content was observed
by Singhal et al.74 Hankare et al.75 studied the electrical prop-
erties of nickel substituted cobalt ferrites and reported that the
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Fig. 1 SEM micrographs of typical Co1
xMnxFe2O4 samples (this gure has been adapted/reproduced from ref. 68 with permission from
Elsevier).
entire ferrite compositions were n-type semi-conductors. Singh
et al.76 synthesized NixCo1
xFe2O4, x 0.0, 0.2, 0.4, 0.6, 0.8, 1.0
and explored their potential for the reduction of 4-nitrophenol
and photo-oxidative degradation of rhodamine B dye. Cobalt
ferrite was found to be inactive for the reduction reaction.
However, the introduction of Ni2+ in cobalt ferrite lattice
resulted in increased catalytic eciency.
The introduction of copper ions in the structure of cobalt
ferrite is expected to modify its structural and magnetic prop-
erties, making it suitable material as sensor and catalyst and for
the treatment of industrial euents. Balavijayalakshmi et al.81
studied the inuence of copper on the magnetic properties of
cobalt ferrite nanoparticles. The authors reported that the
saturation magnetization, remanent magnetization and coer-
civity decreased with increase in copper substitution due to
octahedral site preference and decrease in magneto crystalline
anisotropy respectively. An et al.82 also found similar trend of
magnetic properties with increase in Cu content.
Substitution of zinc into the cobalt ferrite lattice is expected
to produce distorted spinel structures. This is because Zn2+ ions
seek to the tetrahedral sites while Co2+ ions preferentially seek
to the octahedral sites. Therefore, the introduction of zinc in the
cobalt ferrite lattice leads to interesting types of cation distri-
bution over tetrahedral A-sites and octahedral B-sites. From
applications point of view, cobaltzinc ferrites belong to the
class of so ferrites, hence, these are used in transformer cores,
electric motors and generators. Because of their vast applica-
tions, tremendous amount of work on zinc substituted cobalt
ferrites is reported.8398 Nikam et al.83 synthesized zinc
substituted cobalt ferrites and observed that due to replacement
of smaller Co2+ ions (0.72 A) by larger Zn2+ ions (0.74 A), there
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was increase in lattice constant values with increasing Zn2+ ion
substitution. However, the variation of saturation magnetiza-
tion values with increase in Zn2+ ions concentration was found
to be interesting as it was not monotonic and it increased
initially up to x 0.2 and then continuously decreased with
further increase in x. This initial increase was ascribed to Neel's
collinear two-sublattice model and further decrease was
ascribed to three-sublattice model suggested by Yafet-Kittel.
Hassadee et al.84 prepared Co1
xZnxFe2O4 (x 0.00.5) and
observed that the substitution of Co2+ ions by Zn2+ ions led to
increase in lattice parameter from 8.381 A to 8.412 A. The entire
ferrite compositions showed ferrimagnetic behavior. The coer-
civity decreased with increasing Zn2+ ion concentration due to
decrease in magneto-crystalline anisotropy. Deraz and Alari85
synthesized Co1
xZnxFe2O4 (x 0, 0.25, 0.5, 0.75 and 1) and
observed that Zn content was found to aect the morphology of
the sample. The SEM images revealed that the samples had
a spongy, homogenous and fragile network structure contain-
ing voids and pores; which increased with increase in Zn
content as shown in Fig. 2.
Patil et al.86 studied the eect of zinc substitution on the
elastic properties of CoZn ferrites Co1
xZnxFe2O4 (x 0.0,
0.2, 0.4, 0.6, 0.8 and 1.0). The elastic properties were found to
decrease with increase in Zn2+ content. However, the Poisson's
ratios and the corresponding Debye temperature exhibited
a decreasing trend with increasing zinc substitution due to the
fact that as the Zn2+ ion concentration increased, the inter-
atomic binding between various atoms weakened continu-
ously. Shari and Shokrollahi87 synthesized Co1
xZnxFe2O4 (0.5
< x < 0.75) and observed that the lattice parameter, saturation
magnetization, and coercivity decreased with increase in Zn
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Fig. 2 SEM micrographs depicting increasing voids and pores with increasing zinc content in Co1
xZnxFe2O4 (this gure has been adapted/
reproduced from ref. 85 with permission from Elsevier).
content. Also it was interesting to note that the growth of
particles was obstructed by the presence of zinc. So with
increase in Zn content particle sizes decreased which could be
due to dierence in the enthalpies of formation.
Jauhar and Singhal88 synthesized various transition metal
substituted cobalt ferrites CoMxFe2
xO4 (M Cr3+, Ni2+, Cu2+,
Zn2+; 0.2 # x # 1.0) and observed that the saturation magne-
tization decreased with increase in the concentration of tran-
sition metal ion, attributed to their octahedral site preference
and lower magnetic moments as compared to that of Fe3+ ion.
In addition, the catalytic activity was also evaluated and it was
found to be largely dependent upon two factors cation
distribution and presence of oxygen vacancies on the surface of
the ferrite catalyst. The transition metal ions which were known
to exhibit more than one oxidation states may participate in the
cyclic electron process. However, the transition metal ions
exhibiting only one stable oxidation state did not participate
directly in the cyclic electron transfer process, but they inu-
enced the catalytic activity indirectly by changing the cation
distribution of the ferrites.
3.3. Substitution with transition elements of second
transition series
Among the elements of second transition series, the ions which
have been majorly reported to be substituted in the cobalt
ferrite lattice are yttrium, niobium, molybdenum and
cadmium. Yttriumcobalt ferrite Y0.2CoFe1.8O4, was synthe-
sized by Shobana et al.99 and due to octahedral site preference of
Y it possessed an inverse spinel structure. A systematic study on
the yttriumcobalt ferrites was carried out by Meng et al.100 who
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prepared CoFe2
xYxO4 (x 0, 0.1, 0.3 and 0.5). As the concen-
tration of yttrium increased, both the crystallinity and lattice
parameter decreased. This was because more dopant concen-
tration led to a higher potential barrier that rare earth ion had to
overcome for entering the spinel crystal lattice. As a result,
crystal lattice distortion, lower degree of alignment of lattice
fringes and local strains appeared.
Kiran et al.101 synthesized niobium substituted cobalt ferrite
Co1.1Fe1.85Nb0.05O4 and the lattice parameter of niobium
substituted cobalt ferrite was found to be higher than that of
pure cobalt ferrite. However, the saturation magnetization, as
well as the rst order magneto crystalline anisotropy constant of
Co1.1Fe1.85Nb0.05O4 was found to be lower than that of pure
cobalt ferrite. This was attributed to the decrease in the super
exchange interaction and an additional quenching of orbital
angular momentum, due to deviation from octahedral
symmetry.
Heiba et al.102 synthesized molybdenum substituted cobalt
ferrite CoFe2
xMoxO4 (0.0 # x # 0.3). The lattice parameter
decreased linearly with Mo6+ substitution up to x 0.15 and
then non-linearly for x $ 0.2. This variation in lattice parameter
was attributed to the fact that Mo6+ ions replaced Fe3+ ions in
the tetrahedral A-sites up to x 0.15, resulting in a decrease in
the lattice parameter values. For x $ 0.2, Mo6+ ions replaced
Fe3+ in both tetrahedral and octahedral sites. Thus, the lattice
parameter value decreased in a non-linear manner due to
dilution of Fe3+ ions in the B-sublattice.
Cadmium substituted cobalt ferrites Co1
xCdxFe2O4 (x
0 to 1.0), were synthesized by Ghani et al.103 and the lattice
parameter was observed to increase with increase in Cd2+
concentration, due to larger ionic radius of Cd2+ ion as
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compared to Co2+ ion. The saturation magnetization was
maximum for x 0.35 which was explained on the basis of
statistical and non-collinear models. Noor et al.104 also synthe-
sized Co1
xCdxFe2O4 (x 0.01.0). The variation of saturation
magnetization values with increasing Cd2+ concentration
showed interesting behavior. The saturation magnetization
initially increased with increase in Cd2+ concentration upto x
0.4 and thereaer, it decreased. The decrease in saturation
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magnetization values beyond x 0.4 was due to the existence of
Y-K type of magnetic ordering in the lattice, arising out of the
spin-canting phenomenon caused by the presence of Cd2+ ions
possessing the diamagnetic character which disturbed the
parallel arrangement of spin magnetic moments on the B-site
and canting of spin occurred. Similar behavior of saturation
magnetization due to canted spins was observed by Singhal
et al.105
3.4. Substitution with rare earth elements
Present decade has seen a growth in the study of cobalt ferrites
substituted with rare earth metals. Rare earth metals are
interesting ions for substitution in cobalt ferrite lattice because
in rare earth metals, the carriers of magnetism are the 4f elec-
trons. In addition, lanthanoid ions can be isotropic or aniso-
tropic in relation with the variation in the f-electron orbital
conguration to magnetic interactions. By substituting a small
amount of Fe3+ or Co2+ ions by rare earth ions, an appearance of
3d4f coupling takes place.
Various metals belonging to lanthanoids and actinoids like
lanthanum, terbium, neodymium, dysprosium, gadolinium,
samarium, holmium, erbium and praseodymium have been
substituted into cobalt ferrite lattice.106127 For instance, Kahn
and Zhang106 synthesized CoLn0.12Fe1.88O4 (Ln Ce, Sm, Eu,
Gd, Dy or Er) and observed that substitution of Ce3+, Sm3+ and
Eu3+ resulted in decrease in saturation magnetization values as
compared to pure cobalt ferrite. However, the coercivity
increased with substitution with lanthanoid ions as compared
to pure cobalt ferrite. The change in magnetic properties was
attributed not only to the number of unpaired electrons but also
to the strength of spinorbit coupling. Rare earth substituted
cobalt ferrites of the formula CoFe1.9RE0.1O4 (RE La, Ce, Nd,
Sm, Eu, Gd, Tb, Ho) were synthesized by Tahar et al.107 The
lattice parameter was found to be larger in case of rare earth ion
substituted ferrites as compared to pure cobalt ferrite due to the
larger ionic radii of rare earth ions. Existence of super-
paramagnetic relaxations was also observed which indicated
the blocking temperature to be low due to which remanence
was zero for all the samples. Rare earth substituted cobalt
ferrites of the formula CoFe1.8RE0.2O4 (RE Dy, Gd, La) were
synthesized by Dascalu et al.108 The saturation magnetization
decreased while the coercive eld increased with increase in
concentration of rare earth ion due to the weaker nature of
RE3+Fe3+ interaction compared to Fe3+Fe3+ interaction.
Panda et al.109 prepared CoMxFe2
xO4 (M Gd and Pr, x 0,
0.1 and 0.2). The room temperature saturation magnetization
and crystallite size decreased with successive doping. This was
due to the presence of super paramagnetic fractions and spin
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canting at the surface of nanoparticles. Insertion of rare-earth
atoms in the crystal lattice inhibited the grain growth of mate-
rials in a systematic manner. Moreover, the coercivity of
substituted cobalt ferrites was improved. Lanthanum doped
cobalt ferrites, CoLaxFe2
xO4 (x 0, 0.1, 0.15, 0.2), having
improved dielectric and magnetic properties were synthesized
by Kumar et al.110 The lanthanum substituted ferrite samples
exhibited high resistivity of 20.61  106 U cm for x 0.1. This
was ascribed to the fact that La3+ ions block the Verwey's
hopping mechanism resulting in an increase of resistivity.
Cerium substituted cobalt ferrites CoFe2
xCexO4 (x 0.0,
0.01, 0.05, 0.1 and 0.15) were synthesized by Wu et al.111 On
increasing the cerium concentration above 0.05 resulted in the
formation of small amount of CeO2 phase. The synthesized
ferrites exhibited enhanced infrared radiation properties.
Zhao et al.112 synthesized CoFe2
xNdxO4 (x 0.00, 0.10, 0.20)
nanoparticles and found that the crystallite size increased with
increase in Nd3+ concentration. The variation of crystallite size
with increasing temperature was also studied which presented
some fascinating results. As expected, the crystallite size
increased with increase in annealing temperature. However, the
average crystallite size was 10 nm for the entire ferrite
compositions annealed at 600  C which increased to 17 nm
when annealed at 800  C. This was attributed to the fact that
lanthanoid ions have empty or half-lled or fully lled 4f elec-
tron shell with stable structure, so the sample with rare earth
ions has high thermal energy. The bond dissociation energy of
Nd3+O2
(703 kJ mol
1) was larger as compared to that of Fe3+
O2
(409 kJ mol
1). Therefore, it was deduced that more energy
was needed to make Nd3+ ions enter into the lattice. Conse-
quently, Nd3+ substituted ferrites had larger thermal stability.
The properties of CoFe2
xSmxO4 (x 00.4) were studied by
Rashad et al.113 It was found that as the Sm3+ content was
increased, the average crystallite size decreased which was also
related to the increased thermal stability with the introduction
of a rare earth cation. Similar thermal stability was observed by
Guo et al.114 for CoFe2
xSmxO4 (x 00.2). The saturation
magnetization also decreased with increase in Sm3+ concen-
tration, due to smaller magnetic moment of Sm3+ ions.
Gadolinium substituted cobalt ferrites, CoFe2
xGdxO4 (x 0,
0.03, 0.05, 0.07 and 0.1) were synthesized by Zhao et al.115 With
increasing Gd3+ content, the average particle size reduced from
13 nm to 8 nm. The saturation magnetization and coercivity
also decreased with increase in concentration of Gd3+ ions. The
synthesized compositions exhibited a higher adsorption
capacity for Congo red, compared to the undoped ferrite. Pant
et al.116 also synthesized gadolinium substituted cobalt ferrite
nanoparticles of the formula CoGdxFe2
xO4 (x 0.1, 0.3, 0.5).
The XRD studies revealed that the lattice parameter increased
with increase in gadolinium concentration. On the basis of the
FT-IR spectra, it was conrmed that gadolinium ions occupied
octahedral sites of the ferrite sub lattice.
Sodaee et al.117 investigated the role of terbium substitution
on the magnetic properties of cobalt ferrite nanoparticles of the
composition CoFe2
xTbxO4 (x 0, 0.1, 0.2, 0.3, 0.4, 0.5). It was
observed that the saturation magnetization increased with
increase in terbium concentration. The variation of saturation
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magnetization was explained on the basis of exchange interac-
tion among cations distributed over tetrahedral A-sites and
octahedral B-sites of the ferrite sub-lattice. Also the coercivity
decreased with increase in terbium content owing to the
decrease in magneto-crystalline anisotropy. The inuence of
terbium substitution at cobalt site of cobalt ferrite (Co1
xTbx-
Fe2O4 (x 0.0, 0.03, 0.06, 0.09, 0.12 and 0.15)) was investigated
by Khan et al.118 The lattice parameters such as lattice constant,
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cell volume and crystallite size enhanced with increase in
terbium ions concentration. However, there was decrease in
coercivity with substitution of terbium with cobalt.
Dysprosium substituted cobalt ferrites Co1
xDyxFe2O4 were
synthesized by Mohammadifar et al.119 It was found that the
doping of Dy3+ ions led to an increase in the lattice parameter
and the crystallite size. In addition, the substitution could
eectively alter the inversion degree of spinel ferrites and their
magnetic features. The saturation magnetization had
a descending trend with increasing content of Dy3+ ion.
Magnetic and structural properties of dysprosium doped cobalt
ferrites, Co1
xDyxFe2O4 nanoparticles were also studied by
Karimi et al.120 The authors reported a decreasing trend of
saturation magnetization and an increasing behavior for coer-
civity with increasing Dy3+ ion concentration. There was a great
decrease in Curie temperature, with increase in dopant
concentration.
The structural and magnetic properties of holmium
substituted cobalt ferrites CoHoxFe2
xO4 (x 0.000.10) were
studied by Ali et al.121 The samples were prepared by
co-precipitation technique. The authors observed an initial
increase in lattice constant values upto x 0.04, above which
lattice constant decreased. This variation in lattice constant
values was to the possibility that the compression of the spinel
lattice occurred by the formation of intergranular secondary
phase arising out of the dierences in the thermal expansion
coecients. The saturation magnetization decreased while
coercivity increased with increase in Ho3+ substitution due to
the octahedral site occupancy of larger Ho3+ and the presence of
an ultra-thin layer at the grain boundaries which impeded the
domain wall motion. Prathapani et al.122 prepared erbium
doped cobaltferrite (CoFe2
xErxO4, x 0, 0.01, 0.02, 0.03 and
0.04) and observed that at higher Er3+ content (x 0.03 and
0.04), there was emergence of orthoferrite phase of ErFeO3.
Also, the authors observed an increase in lattice parameter with
the substitution of Er3+ ions in the cobalt ferrite lattice, due to
larger size of Er3+ than Fe3+. However, the crystallite sizes of Er3+
doped cobalt ferrites were lower than pure cobalt ferrite.
Magnetic studies revealed a marginal increase in magnetization
followed by a decrease which was ascribed to rearrangement of
cation distribution upon substitution of Er3+ ions into cobalt
ferrite lattice.
3.5. Substitution of more than one element into the cobalt
ferrite lattice
The cobalt ferrite lattice allows the incorporation of more than
one metal ion into its lattice. This gives rise to new materials
with interesting and unique properties. Thus, substituted
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cobalt ferrites having a wide range of properties, for use in
various spheres of science and technology, can be prepared.
Tremendous studies have been carried out on cobalt ferrite
substituted by more than one metal ion.128143 When two metal
ions are substituted into cobalt ferrite lattice, then some
new behavior may also be observed. For example, CrCd
co-substituted cobalt ferrite show a lower saturation magneti-
zation values as compared to cadmium substituted cobalt
ferrites.128 This might be due to the reason that Cd2+ ion has
tendency to go to the tetrahedral sites of the ferrite sub-lattice.
However, when Cd2+ ion is co-substituted along with Cr3+ ion
into the cobalt ferrite lattice, then some Cd2+ ions also occupy
octahedral sites of the ferrite sub-lattice.
Jauhar et al.129 prepared CoCd0.4CrxFe1.6
xO4, (x 0.1, 0.2,
0.3, 0.4, 0.5 and 0.6). The magnetic properties, like saturation
magnetization and coercivity, showed a decreasing trend with
increase in Cr3+ concentration. This suggested that chromium
ions occupied the octahedral sites of the ferrite sub-lattice. Also
the d.c. resistivity increased with Cr3+ concentration, suggesting
occupancy of Cr3+ ions in the B-sites which led to the dilution of
Fe2+Fe3+ conduction. The properties of MnCd co-substituted
cobalt ferrites were studied by Singhal et al.130 With the
substitution of Mn3+ ions in cobaltcadmium ferrites, the
magnetic properties, like saturation magnetization and coer-
civity showed a decreasing trend while the d.c. resistivity
increased, suggesting occupancy of Mn3+ ions in the octahedral
B-sites.
Recently, Rezlescu et al.131 synthesized Ni0.5Co0.5ScxFe2
xO4
(x 0, 0.05, 0.1 and 0.2) and investigated their catalytic activity
towards the combustion of acetone, propanone and benzene.
The authors observed that the introduction of Sc3+ ions into the
NiCo ferrite has favorable eect on catalytic activity and
amongst various synthesized ferrites, Ni0.5Co0.5Sc0.2Fe1.8O4 was
most procient catalyst. Ce3+ substituted CoCr ferrite
(CoCr0.04CexFe1.96
xO4, x 0.00.1) were synthesized by Mus-
tafa et al.132 There was an increase in crystallite size from
42.2 nm to 106 nm with increase in Ce3+ substitution. Also,
based upon the excellent results obtained for magnetic
measurements, authors commented that synthesized materials
are potential candidates for magnetic recording media, security,
switching and high frequency applications.
Thus, by substituting two or more ions in the cobalt ferrite
lattice, new materials with tunable physical and chemical
properties can be obtained, which are of great use in industry.
4. Advances in research on cobalt
ferrite
Reports available on cobalt ferrite have explored its many facets.
Many new synthetic methods have been developed, which lead
to the development of cobalt ferrite with polished properties. In
addition, the application studies of cobalt ferrite have been
explored in various growing elds such in biomedicine, catal-
ysis, as permanent magnets and as sensors. Also, a large volume
of work is reported on the composites of cobalt ferrite with
other inorganic compounds. These are discussed below:
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4.1. Development of new synthetic methods The eect of fuel characteristics on the processing of nano-
sized cobalt ferrite ne powders, synthesized by combustion
Cobalt ferrite with improved properties has been reported to be
technique, was studied by Salunkhe et al.149 The authors re-
synthesized with various new methods. For instance, Verma and
ported that the phase stability, morphology, microstructure and
Pravarthana144 used a one-pot method to synthesize highly mono-
crystallite size depended on glycine to nitrate molar ratio. The
dispersed nano-crystals of cobalt ferrite. The authors utilized
grain size and porosity increased with increase in glycine to
a strong polar organic solvent, N-methyl-2-pyrrolidone and an
nitrate molar ratio. Naidek et al.150 studied the structure and
equimolar mixture of oleic acid and oleylamine to coat the
magnetic nano-crystals. The use of N-methyl-2-pyrrolidone for morphology of spinel ferrites chemically synthesized by sol-
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synthesizing ferrite was introduced for the rst time. The advan- vothermal decomposition of trimetallic acetate complex
precursors in benzyl ether, in the presence of oleic acid and
tages associated with this solvent are its stability at low tempera-
oleylamine, using 1,2-dodecanediol as the reducing agent. The
ture, low ammability, low volatility and no clear toxicity prole.
ferrite nanoparticles were homogeneous and had a narrow size
The reaction was carried out at a low temperature of 200  C
distribution, as compared to ferrites synthesized using mixed
under argon atmosphere. This was a relatively new strategy to
metal salts. The dierences in the morphological characteris-
obtain monodispersed nano-crystals using a bottom-up approach.
tics were attributed to the dierent mechanism of nucleation,
A facile synthesis of mono-disperse cobalt ferrite nano-
crystals was reported by Salih et al.145 Cobalt ferrite nano- proposed on the basis of thermogravimetric data and is shown
particles in the range of 35 nm were synthesized starting from in Fig. 3. Thus, the ferrites synthesized from heterometallic
complexes had dierent morphology, due to which their
inexpensive metal powders and octanoic acid by thermolysis in
magnetic properties were closer to the superparamagnetic
a high boiling solvent. Due to their small size, the nanoparticles
behavior. Synthesis of well-dispersed cobalt ferrite nano-
exhibited super paramagnetic behavior. The authors also re-
particles via polyvinyl alcohol (PVA) assisted low temperature
ported that the particle size may be increased with a prolonged
solid state process was carried out by Qin et al.151 The eect of
procedure in accordance with Ostwald ripening process. The
amount of PVA added and calcination temperature on the
advantage of this method was that a uniform particle size was
obtained and this method did not require any protection from properties was also investigated. It was proposed that the
oxygen and moisture. The eect of high energy ball-milling time addition of PVA augments the contact and reaction of the
reactants inter particles, and breaks up the three dimensional
on structural and magnetic properties of nanocrystalline cobalt
network of products, leading to the formation of well-dispersed
ferrite powders was also reported by Cedeno-Mattei et al.146 The
cobalt ferrite nanoparticles.
cobalt ferrite nanocrystals were synthesized by conventional co-
An easy, ecient and reproducible one pot synthetic meth-
precipitation method and were treated with high energy ball
odology to obtain cobalt ferrite nanoparticles was reported by
milling. Aer 5 h of ball milling, the coercivity increased from
Perez-Mirabet et al.,152 by the thermal decomposition of
394 to 560 Oe. The preparation of cobalt ferrite from thermal
decomposition of cobalt tris(malonato)ferrate(III) trihydrate Fe(acac)3 and Co(acac)2 in oleylamine. The role of oleylamine is
precursor was reported by Randhawa et al.147 The synthesis of to behave as a capping ligand, by producing stable colloidal
dispersions of nanoparticles in non-polar solvents. The
cobalt ferrite was carried out via a series of steps involved in the
synthetic procedure for the synthesis of ferrites is represented
reaction. Firstly, the starting precursor was decomposed to yield
in Fig. 4. A unique method for the synthesis of cobalt ferrite by
cobalt malonate and iron(III) malonate intermediates at 205  C.
a simple aloe vera plant extracted solution via hydrothermal
At 325  C, there was decomposition of these species which
route was reported by Phumying et al.153 This biosynthetic route
yielded CoO and a-Fe2O3. Finally, cobalt ferrite was obtained by
provides high yield of nanoparticles, with a crystalline struc-
solid state reaction between Fe2O3 and CoO at 380  C.
An interesting one pot synthesis of shape and size controlled ture. Khandekar et al.154 studied the role of fuels (glycine and
cobalt ferrite was reported by Moriya et al.148 Nanoparticles of size hexamethylene tetramine (HMT)) on intrinsic and extrinsic
properties of cobalt ferrite synthesized via combustion method.
greater than 20 nm were obtained by the thermolysis of mixed
It was reported that the sample prepared using glycine as fuel
valence triiron complexes and heterotrimetallic complexes as
was dense while the one synthesized using HMT had a porous
a precursor using benzilic acid as a capping agent. The
structure. Also the d.c. resistivity of ferrite synthesized using
morphology of the resultant nano-crystals was strongly dependent
HMT was higher than the one synthesized using glycine.
on the molar ratio of benzilic acid to the precursor complexes.
Pan et al.155 synthesized cobalt ferrite nano-bres and
With the increase of benzilic acid concentration, the morphology
of nanocrystals changed from truncated octahedron to cube. Raut annealed them at varying heating rates. The authors reported
et al.27 irradiated CoZn spinel ferrite nanoparticles (Co1
xZnx- that the morphology of cobalt ferrite was dependent on the
heating rate. The morphology was continuous brous for low
Fe2O4, x 0.0, 0.2, 0.4, 0.6, 0.8 and 1.0) with Co60 gamma rays and
heating rate and packed crystallites for high heating rate.
thereaer compared their structural and magnetic properties with
Increasing heating rate also increased the diameter (Fig. 5).
pristine samples. Gamma irradiation resulted in generation of
Recently, hollow nanomaterials have attracted broad attention
crystal defects in the nanoferrites. The authors observed an
due to their superior properties. These have proven to be
increase in lattice constant values and a decrease in crystallite size
promising materials for applications like drug delivery, catal-
X-ray density and porosity upon gamma irradiation for all the
samples. ysis, energy storage and gas sensing. Multiple shell hollow
cobalt ferrite spheres were synthesized by Zhang et al.156 using

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Fig. 3 Series of reactions proposed for thermal decomposition of the heterometallic acetate complexes (this gure has been adapted/repro-
duced from ref. 150 with permission from Elsevier).
carbon spheres as templates. The proposed formation mecha-
nism is shown in Fig. 6. The resultant multiple shell hollow
cobalt ferrite spheres showed enhanced textural, drug capacity
and sustained drug release properties compared to solid
Fig. 4 Synthetic procedure to obtain MFe2O4 nanoparticles in oleyl-
amine (this gure has been adapted/reproduced from ref. 152 with
permission from Elsevier).
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nanoparticles, owing to their large surface area and inter-
connected macropores.
A one step synthesis of spinel ferrite hollow spheres by
template free solvothermal method in ethylene glycol was re-
ported by Li et al.157 The hollow spheres were monodispersed
with an average diameter of 360 nm, as shown by their TEM
images (Fig. 7(a)). Ethylene glycol was reported to play a key role
in determining the morphology of hollow spheres. This was
conrmed by carrying out the same reaction in aqueous
medium. The morphology of the ferrite particles so obtained
was completely dierent from that of hollow spheres. The
ferrite nanoparticles looked like octahedral crystals as shown in
FE-SEM images given in Fig. 7(b). Abbas et al.158 synthesized
nanospheres and nano-cubes of cobalt ferrite using sonication
in association with co-precipitation methodology called as
sonochemical technique. Dierent morphological structures
(spherical and cubic) were obtained by changing the solvent
medium as shown in the TEM images in Fig. 8(a) and (b).
Thus, various new methods have given rise to the develop-
ment of cobalt ferrite with varying shapes and sizes attributing
unique properties and enhancing the range of application of
these nanoparticles.
4.2. Composites of cobalt ferrite
Pristine magnetic nanoparticles are prone to agglomeration due
to their large surface energy and strong magnetic interac-
tions.159 Therefore, supporting them on an inert material
increases their dispersibility, stability and resistance to
agglomeration. In recent years, there is a growing interest in
synthesis of composites of cobalt ferrites with inorganic/organic
compounds. This is because such composites exhibit potential
applications in various chemical reactions, mainly due to high
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Fig. 5 SEM images of cobalt ferrite with dierent heating rates of annealing (A) 1  C min
1, (B) 3  C min
1, (C) 4  C min
1, (D) 5  C min
1, (E) 6  C
min
1 (this gure has been adapted/reproduced from ref. 155 with permission from Elsevier).
dispersibility, stability and improved physical and chemical
properties when functionalized or supported on inert/inorganic
materials. A large amount of work has been reported on
composites of cobalt ferrite with dierent materials. Recently,
Tong et al.160 synthesized silica supported cobalt ferrite complex
oxides, CoFe2O4/SiO2 with dierent cobalt ferrite loading of 5,
Fig. 6 The formation mechanism of multiple shell hollow structure
(this gure has been adapted/reproduced from ref. 156 with permis-
sion from Elsevier).
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10, 20 and 50% by solgel auto-combustion method. The
synthesized samples were used to catalyze the oxidation of
cyclohexane with molecular oxygen (Scheme 2). The authors re-
ported that all the silica supported catalysts exhibit a higher
catalytic activity as compared to pure cobalt ferrite. Highest
catalytic activity was observed with 5% loading of CoFe2O4/SiO2
with a turnover number of 4181 and selectivity of 95.4%. Similarly,
titaniasilica (TiO2SiO2) coated cobalt ferrite nanocomposites
have been fabricated by Harraz et al.161 The synthesized nano-
composites were found to possess outstanding catalytic activity
for the degradation of methylene blue dye and catalytic activity
was dependent upon catalyst loading, solution pH and concen-
tration of dye. Also, due to magnetic nature of catalyst, it could be
easily recovered from the reaction mixture and could be reused.
Recently, Haer et al.162 synthesized periodically ordered
BaTiO3/CoFe2O4 multiferroic nanostructured composite. In the
rst step, mesoporous cobalt ferrite was prepared. Subse-
quently, BaTiO3 was created inside the pores of cobalt ferrite by
the citrate route, resulting in a well ordered composite material
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Fig. 7 (a) TEM images of CoFe2O4 hollow spheres synthesized in ethylene glycol solution and (b) FE-SEM images of CoFe2O4 synthesized in
water solution (this gure has been adapted/reproduced from ref. 157 with permission from Elsevier).

Fig. 8 TEM images of cobalt ferrite nanoparticles synthesized in (a) aqueous medium, and (b) alcoholic medium (this gure has been adapted/
reproduced from ref. 158 with permission from Elsevier).

Scheme 2 Oxidation of cyclohexane with molecular oxygen (this gure has been adapted/reproduced from ref. 160 with permission from
American Chemical Society).

for both phases, as shown in the Fig. 9. The composite showed
ferrimagnetic behavior. Based on this synthesis concept, new
perspectives arise for the preparation of multiferroic composite
materials. Chaudhuri and Mandal163 synthesized mixture and
nanocomposites of CoFe2O4 : BaTiO3, having 1 : 1 weight ratio,
using a combination of hydrothermal and sol gel techniques.
TEM studies indicated the formation of coreshell structure in
the case of nanocomposites. These results were further
corroborated by zero-eld-cooled and eld-cooled magnetiza-
tion vs. temperature curves in the presence of a magnetic eld of
100 Oe. Magnetic studies revealed that magnetoelectric coe-
cient of the coreshell structures was 35 times higher than that
of the physical mixture of sample.
Chen et al.164 established both theoretically and experimen-
tally, that room-temperature manipulation of the nanoscale
magnetization reversal can be achieved by merely applying
external electric elds onto Fe-decient cobalt ferrite thin lms.
For the experimental setup the authors rst deposited a SrRuO3
thin lm on a commercially available SrTiO3 (110) substrate
with a pulsed laser deposition system. The CoFe2
xO4 thin lm
was then deposited on the SrRuO3 thin lm. First-principles
calculation results suggested that the observed magnetization
reversal could be due to the reversible migration and redistri-
bution of Co2+ ions between Fe vacancies and was further
assisted by the presence of oxygen vacancies, which in turn
resulted in the unidirectional magnetic anisotropy of the
sample along the (110) directions. So the application of electric
elds with appropriate polarity and amplitude could modulate
the size of magnetic domains with dierent magnetizations.
Such a concept of modulating magnetization by nanoscale ion

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Fig. 9 Schematic synthesis of a nanostructured BaTiO3/CoFe2O4 composite (this gure has been adapted/reproduced from ref. 162 with
permission from Elsevier).
manipulation through electrical means can help to realize
dierent applications.
Yan et al.165 synthesized cobalt ferrite nanoparticles conned
within mesoporous silica SBA-15 and studied their magnetic
properties. The synthesis of cobalt ferrite nanoparticles inside
the mesoporous channels was done by impregnation of cobalt
salt and iron salt precursors into the channels of SBA-15, fol-
lowed by calcinations at dierent temperatures in air. These
materials exhibited open, ordered, 2D hexagonal frameworks.
The highly ordered mesoporous SBA-15 played an important
role in determining the magnetic properties of CoFe2O4/SiO2
composites. Borgohain et al.166 reported the synthesis of nano-
crystalline cobalt ferrite embedded one-dimensional ZnO het-
erostructure via PEG mediated sono-chemical route. The band
gap of the nanocomposite (4.5 eV) was found to be higher than
pure ZnO nanoparticles (3.3 eV). This one-dimensional
CoFe2O4ZnO heterostructure possessed a higher photo-
catalytic activity that ZnO. This was demonstrated for the pho-
tocatalytic degradation of phenolphthalein under UV radiation
with degradation of 89% in 1 h.
Sathishkumar et al.167 studied the catalytic activity of
CoFe2O4/TiO2 composites for the photocatalytic degradation of
reactive red 120 in aqueous solutions in the presence and
absence of electron acceptors. The synthesized nano-catalysts
showed higher eciency towards the photocatalytic degrada-
tion of reactive red 120 and the use of electron acceptors such as
peroxomonosulfate, peroxodisulfate and hydrogen peroxide,
led to a synergic enhancement in the photocatalytic degrada-
tion. Likewise, Gaikwad et al.168 utilized Fe, N co-doped TiO2
CoFe2O4 nanocomposite for the degradation of methyl orange
dye. The authors observed an enhancement in photocatalytic
performance of nanocomposite as compared to TiO2. This
enhancement in photocatalytic performance was attributed to
increased optical absorption property of nanocomposite as
compared to TiO2.
Nowadays, there is an increasing interest in the synthesis of
ferrite/Multi-Walled Carbon Nano-Tubes (MWCNTs) because of
the unique properties associated with such systems, attributed to
their large surface area. Recently, the synthesis of Zn1
xCoxFe2O4/
MWCNTs (x 0.0, 0.2, 0.4, 0.6 and 0.8) was reported by Singh
et al.169 The formation of composites was conrmed from the
TEM images. The authors reported super-paramagnetic behavior
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of the synthesized composites which was attributed to the size of
ferrite particles being in the critical domain. The morphology
and structure of electrospun CoFe2O4/MWCNTs composite bres
was studied by Lamastra et al.170 The amount of nano-tubes used
was 1 wt% with respect to cobalt ferrite. The average diameter of
as spun nano-bres was 100 nm. It was concluded that the
presence of nanotubes did not aect the cubic spinel phase
formation and structure.
In recent years, the research interest is also driing towards
the composites of cobalt ferrite with graphene. This is because
graphene sheets provide a large surface area, thereby, resulting
in interesting modications in the properties of cobalt ferrite.
For example, Li et al.171 synthesized magnetic cobalt ferrite-
functionalized graphene sheets via a facile hydrothermal
method and studied their adsorption properties for methyl
orange from aqueous solutions. The adsorption of methyl
orange on cobalt ferritegraphene composites followed pseudo
second order kinetic model and the adsorption capacity was as
high as 71.54 mg g
1.
Li et al.172 also carried out a one-step synthesis of cobalt
ferrite/graphene nanocomposites. The method involved two
processes occurring simultaneously: co-precipitation of Co2+
and Fe2+ ions on the surface of graphene oxide by using urea as
precipitant; and in situ reduction of graphene oxide. A sche-
matic diagram representing synthesis of composites is shown in
Scheme 3. The as synthesized nanocomposites exhibited a high
specic reversible capacity up to 937.73 mA h g
1, with high
charge/discharge reversibility. A high performance and recy-
clable visible light photocatalysts were synthesized by Fu et al.173
by the combination of cobalt ferrite and graphene. The authors
reported that the combination of cobalt ferrite nanoparticles
with graphene resulted in a dramatic conversion of inert cobalt
ferrite into a highly active catalyst for degradation of methylene
blue, rhodamine B, methyl orange, active black BL-G and active
red RGB under visible light irradiation. The proposed mecha-
nism for the enhanced photocatalytic activity of cobalt ferrite
graphene composite is shown in Fig. 10.
One-pot controllable synthesis of ower like CoFe2O4/
FeOOH nanocomposites was reported for high performance
supercapacitors.174 The ower shaped nanostructures were ob-
tained by tailoring the concentration of urea. These composites
exhibited a specic capacitance of 332.4 F g
1 at the current
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density of 0.5 A g
1, and excellent cycling stability (91.3%
retention aer 1000 cycles, 5 A g
1). A magnetically responsive
three component nanocomposite consisting of CoFe2O4, poly-
aniline (PANI) and nano-silver was prepared by Kooti et al.175
The nanocomposite showed superior antibacterial activity as
compared to CoFe2O4 and CoFe2O4/PANI composite against E.
coli and S. aureus. Thus, these were proved to exhibit broad
spectrum antibacterial activity against Gram positive and Gram
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negative bacteria. On the similar lines, same authors synthe-
sized novel CoFe2O4/SiO2/Ag magnetic nanocomposites. The
antibacterial activity of nanocomposites was investigated
against Gram-positive and Gram-negative bacteria. The authors
observed an enhancement in bactericidal eciency of nano-
composites, when these were used in combination with strep-
tomycin antibiotic. Therefore, this synergistic eect between
nanocomposites and streptomycin provides a means for an
ecient antibacterial activity against dierent bacteria.176
A kind of magnetic multiple functional group nano-
composites, chitosanEDTA enwrapped cobalt ferrite nano-
particles were synthesized by a facile zero length emulsion
cross-linking process by Qin et al.177 Cobalt ferrite was used as
Scheme 3 Schematic illustration of the synthesis of cobalt ferrite/graphene nanocomposites (this gure has been adapted/reproduced from ref.
172 with permission from Elsevier).
Fig. 10 Proposed mechanism of photocatalytic activity enhancement of cobalt ferrite/graphene composites (this gure has been adapted/
reproduced from ref. 173 with permission from Elsevier).
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magnetic core and 1-ethyl-3-(3-dimethylaminopropyl)
carbodiimide hydrochloride (EDAC) was used as a cross
linker, integrating amino group of chitosan and carboxyl group
of EDTA. Further, the nanocomposites were synthesized by
using variable ratios of EDTA, EDAC and NH2 group of chitosan
which was found to aect the magnetic characteristics.
The catalytic activity of nickel hydroxide/cobalt ferrite
magnetic nanocatalyst for alcohol oxidation was studied by
Bhat et al.178 The authors used a surfactant to achieve a high
surface area of 120.94 m2 g
1. An improved catalytic activity and
selectivity were obtained by synergic eect of transition metal
hydroxide on nano cobalt ferrite. An interesting work was re-
ported by Jacob et al.179 who prepared ZnO and cobalt ferrite
based multiphase adsorbent system for purication of water
containing both cationic and anionic dyes. The primary mech-
anism of adsorption was proposed to be lm diusion.
Mirzaee et al.180 investigated experimentally as well as theo-
retically magnetic properties of CoFe2O4/PVA nanocomposites.
The experimental results and Monte Carlo simulation revealed
that saturation magnetization of nanocomposites was signi-
cantly smaller than bulk and bare cobalt ferrite nanoparticles.
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The authors ascribed this decrease in value of saturation
magnetization to the fact that polymeric matrix interact with
surface of cobalt ferrite nanoparticles, thereby making them
non-interacting.
4.3. Cobalt ferrites as permanent magnets
With the emergence of ferrite nanoparticles there is an
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increasing interest in their magnetic characteristics because of
their broad applications in several technological elds
including permanent magnets, magnetic uids, magnetic drug
delivery, microwave devices, and high density information
storage. The properties of nanosized magnetic materials
depend strongly on the shape and size. Furthermore, the
interaction between the particles can strongly inuence their
magnetic properties. The great interest in nanosized materials
in recent years is due to the possibility to modify the properties
by the control of the size and shape and cation distribution.181
Cobalt ferrite nanostructures have opened a new gateway to be
used as permanent magnets as it duplicates the properties of
AlNiCo permanent magnet alloys with quite a good coercivity
and being light in weight.182 Many researchers have explored the
application of cobalt ferrite nanostructures with dierent
modications, as permanent magnets.
Lopez-Ortega et al.45 presented a detailed magnetic charac-
terization of a series of cobalt ferrite nanoparticles with size
ranging between 4 to 60 nm. The magnetic properties were
found to exhibit a size and morphology dependent behavior and
explored the synthesized samples for the best performance as
permanent magnet. Saturation and remnant magnetization
increased monotonously with size, reaching a constant value
above 20 nm and the coercive eld exhibited a nonmonotonic
behavior with two distinct maxima values for low and room
temperature, respectively. Also, (BH)max product was evaluated
as score for permanent magnet application which was found to
be very good i.e. 2.1 MGOe (18 kJ m
3) for 40 nm sized nano-
particles. In continuation to this work Lottini et al.183 further
suggested a new strategy for rare-earth free permanent magnets
via coreshell structures of antiferromagnetic/ferrimagnetic
materials of formula Co0.3Fe0.7O/Co0.6Fe2.4O4. The sharp inter-
face, the high structural matching between both phases gave
rise to very good exchange bias (HE) value of 8.6 kOe and
a strongly enhanced coercive eld (HC). So biasing has been
demonstrated to be a powerful strategy for the improvement of
rare-earth free permanent magnets.
Liu and Ding184 carried out a detailed study on the micro-
structure evolution during mechanical milling and its eect on
magnetic properties. The initial grain/particle size played an
important role in the microstructure evolution. A high coercivity
of up to 5.1 kOe was accompanied by a relatively large residual
strain, probably due to the stress anisotropy and pinning eect.
Chinnasamy et al.185 synthesized cobalt ferrite particles with
diameters ranging from a few microns to about 15 nm by using
the modied oxidation method. The eect of the concentration
of the oxidizing agent such as the nitrate ions, and the addition
of ferric ions from the very beginning of the reaction on the size
and magnetic properties of the particles was studied in detail.
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The cobalt ferrite particles synthesized under optimum condi-
tions had an average grain size of 36 nm and showed coercivity
as high as 2020 Oe and squareness ratio of 0.53 under a 1.5 T
applied magnetic eld at room temperature. Ponce et al.186
synthesized cobalt ferrite nanoparticles via mechanical milling
using dierent grinding balls. The permanent magnetic prop-
erties in the samples were induced with the help of mechanical
milling. The non-milled sample presented coercivity of about
1.9 kOe, saturation magnetization of 69.5 emu g
1, and
a remanence ratio of 0.42. Aer milling, two samples attained
coercivity of 4.2 and 4.1 kOe, and saturation magnetization of
67.0 and 71.4 emu g
1 respectively. The remanence ratio MR/MS
for these samples increase to 0.49 and 0.51, respectively.
Pedrosa et al.187 synthesized nanocrystalline Coferrite
powders with tuneable magnetic properties by using co-
precipitation and a novel ash-milling route. For the very rst
time, milling time of as short as a few minutes was reported to
be sucient to rene microstructure and to induce microstrain,
which provided a 5-fold increase in coercivity. This was achieved
with no compositional change during processing, but exclu-
sively through microstructural modication. The eciency of
this process and its feasible scalability pave the way for devel-
opment of Coferrite powders for permanent magnet
applications.
Cobalt ions were also found to improve the permanent
magnet characteristics of the sample when introduced in to the
lattice of hard ferrites such as lanthanum and strontium
ferrites.188,189
4.4. Catalytic properties of cobalt ferrite
In recent years, cobalt ferrite has emerged as a potential
heterogeneous catalyst in various chemical reactions. It oers
enhanced catalytic activities compared to the corresponding
single component metal oxides. This is because metal oxides
are susceptible to acid and alkali attacks. Ferrites, however, are
chemically more stable and are resistant towards such
substances.190199 Cobalt ferrite is a preferred heterogeneous
catalyst because it is magnetically separable; therefore, can be
easily removed from reaction medium. In addition, it can be
reused many times without any signicant loss of catalytic
activity. Nordhei et al.200 reported the use of hydrogen reduced
cobalt ferrite for the decomposition of carbon dioxide at 500  C.
The authors reported that the spinel structure broke down and
iron(II) oxide was formed as an intermediate. Carbon dioxide
produced carbon monoxide through oxidation of iron(II).
Ren et al.201 investigated the degradation of di-n-butyl phtha-
late using cobalt ferrite nanoparticles. The catalytic activity was
investigated in peroxymonosulfate as oxidation system, which
resulted in the generation of sulfate radicals. The synthesized
cobalt ferrite nanoparticles oered good stability and could be
reused for seven times. Similarly, degradation of dimethyl
phthalate was investigated by Xu et al.202 using graphene-based
cobalt ferrite as an activator of peroxymonosulfate. The authors
observed that graphene-based cobalt ferrite was more ecient
catalyst than cobalt ferrite. Ai et al.203 reported the removal of
methylene blue from colored water using activated carbon/cobalt
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ferrite/alginate composite beads as adsorbent. The kinetic
studies revealed that the adsorption followed the pseudo-second
order kinetic model. In addition, the prepared magnetic beads
possessed high magnetic sensitivity under an external magnetic
eld, which provided an easy and ecient way to separate the
beads from aqueous solution. The removal of methylene blue in
the presence of H2O2 catalyzed by cobalt ferrite was also reported
by Feng et al.204 The surface functionalization rendered the
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hydrophobic nanoparticles water soluble, which made the
nanoparticles suitable for catalytic applications. The synthesized
ferrites exhibited excellent activity in the oxidation of methylene
blue dye, and the nanoparticles could be easily separated from
the medium magnetically.
Dey et al.205 investigated adsorption of arsenic from water
using cobalt ferrite nanoparticles aggregated schwertmannite.
This adsorbent system was found to adsorb more than 95%
arsenic in 240 min. Also, the adsorption was found to be
dependent upon adsorbent mass, pH of the medium, temper-
ature and presence of co-anions (such as phosphate ions).
Moreover, thermodynamic studies revealed the adsorption
behavior to be physisorption with an adsorption capacity of
1011 mg g
1. Recently, Zhao et al.206 synthesized cobalt ferrite
chitosan sulfonic acid nanoparticles (CoFe2O4CSSO3H) using
a two-step process. The authors used the synthesized CoFe2O4
CSSO3H samples for green and ecient synthesis of indazole
[2,1-b]phthalazine-triones. The authors observed that reaction
proceeded smoothly in presence of CoFe2O4CSSO3H under
solvent-free conditions in very short reaction times. Dumitru
et al.207 reported the use of mesoporous cobalt ferrite as an
ecient catalyst for the methane combustion reaction. The
cobalt ferrite exhibited catalytic activity similar to that of plat-
inum. Another interesting work on the catalytic activity of cobalt
ferriteAPTESPd (APTES: 3-aminopropyltriethoxysilane) was
reported by Demirelli et al.208 The authors studied the catalytic
activity of CoFe2O4APTESPd magnetic recyclable catalyst, for
reduction reactions using NaBH4. The catalyst exhibited a high
catalytic activity in the reduction of 4-nitroaniline, 1,3-dinitro-
benzene and cyclohexanone in liquid phase.
A magnetic cobalt ferrite nanoparticle immobilized diamine
N-sulfamic acid (CoFe2O4@SiO2DASA), synthesized by Zhao
et al.209 was used as ecient heterogeneous catalyst for the
synthesis of amides from alcohols and nitriles via the Ritter
reaction under solvent free conditions. A simple Ritter reaction
is shown in Scheme 4. The advantage of using cobalt ferrite is
that it makes the catalyst magnetically recoverable which could
be used several times without any loss of catalytic activity.
Another reaction in which cobalt ferrite is reported to be used as
catalyst is the production of hydrogen gas from alcohols. The
Scheme 4 Synthesis of amides via Ritter reaction (this gure has been adapted/reproduced from ref. 209 with permission from Elsevier).
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production of hydrogen from alcohols is a desired process
because of the high hydrogen to carbon atomic ratios of alco-
hols. Cocchi et al.210 reported the production of hydrogen from
methanol using this process. The authors chose methanol for
generation of hydrogen because it produces less amount of CO
gas. Similarly, Genova et al.211 synthesized cobalt ferrite nano-
particles hosted in activated carbon (prepared from peach
shells) for hydrogen production from methanol.
Three dimensional cobalt ferrite superstructures were
prepared by Jia et al.212 by the controlled thermal decomposition
of the complex oxalate, which were obtained by poval mediated
precipitation reaction. The SEM images of the synthesized
structures showed bow-knot like cobalt ferrite nanostructures
self assembled by nano-rods as shown in Fig. 11. The catalytic
properties of as-synthesized superstructure were also studied.
The hierarchal structures showed better catalytic activity for
ammonium perchlorate by decreasing its decomposition
temperature to as low as 290  C. Cobalt ferrite nanoparticles
synthesized by co-precipitation method, were reported to work
as ecient catalysts for click synthesis of arylidene barbituric
acid derivatives at room temperature.213 The advantages of this
synthesis were short reaction time, high turnover frequency,
simple work up process, a clean reaction, non-toxic reagents, an
aqueous medium, recovery/recyclability of catalyst, ecofriendly
synthesis and excellent yield of products.
Cobalt ferrite nanoparticles synthesized using a combined
sonochemical and co-precipitation technique in aqueous
medium, were utilized as a reusable catalyst for Knoevenagel
reaction in aqueous ethanol (Scheme 5).214 The authors reported
a high yield of products within a very short time in the presence
of just 5 mmol% of catalyst. The eect of morphology on the
photocatalytic activity of cobalt ferrite in phenol methylation
reaction was studied by Ballarini et al.215 A series of cobalt ferrite
nano particles were prepared with tunable diameters spanning
750 nm and were employed in the methylation of phenol to form
cresol (Scheme 6). The catalytic activity showed a pronounced
dependence on particle size, with smaller nanoparticles exhibit-
ing excellent regio- and chemo-selectivity to o-cresol at around
300  C. Increasing either particle size or reaction temperature
promoted methanol decomposition.
Recently, Chagas et al.216 utilized cobalt ferrite nanoparticles
for the oxidation of CO. The authors reported high catalytic
activity of cobalt ferrite on deep CO removal in hydrogen-rich
stream at 250  C during 30 h. Gaikwad et al.168 synthesized
cobalt ferrite coupled Fe and N co-doped TiO2 and found that
photocatalytic performance of the composite was better in
comparison to TiO2 but not doped TiO2. However, the catalyst
had the advantage of magnetic separation. Amine functionalized
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Fig. 11 SEM images of CoFe2(C2O4)3$6H2O precursor observed from various magnication size (a and b) side direction (c) and front direction (d)
(this gure has been adapted/reproduced from ref. 212 with permission from Elsevier).

Scheme 5 Knoevenagel condensation reaction (this gure has been adapted/reproduced from ref. 214 with permission from Elsevier).

cobalt ferrite (AF-CoFe2O4) magnetic nanoparticles (MNPs) were
used for immobilization of cellulase enzyme via coupling reac-
tion. The results revealed that the immobilized cellulase had
higher thermal stability than free cellulose.217 Multi-walled
carbon nanotubes (CNTs) decorated with dierent ferrites was
used under heterogeneous conditions in the dehydration of
fructose by Ranganath et al.218 Inverse spinels, such as cobalt
ferrite (CoFe2O4) and magnetite (Fe3O4), decorated on CNTs
showed better performance than normal spinel such as zinc
ferrite (ZnFe2O4)-decorated CNTs. An ecient method for the
synthesis of pyranoquinoline derivatives using nano cobalt
ferrite as heterogeneous catalyst was developed by Bandaru
et al.219 This method had the advantage of improved yield of
Scheme 6 Methylation of phenol to form cresol (this gure has been
adapted/reproduced from ref. 215 with permission from Elsevier).
products, microwave assisted reaction, less reaction times, clean
and facile separation and reusability of the catalyst. Paul et al.220
presented a rst-ever report in which CoFe2O4 nanoparticles
were used as a catalyst for oxidation of alcohols to aldehydes by
periodic acid and the catalyst eciency was found to be very
high. Also, the CoFe2O4 nanoparticles performance was studied
in the oxidation of benzyl alcohol to benzaldehyde and under
optimum conditions, >99% conversation with benzaldehyde as
the only product, was obtained. The nanocatalyst was also e-
ciently used for the reduction of 4-nitrophenol, Congo red,
methylene blue in water at room temperature.221
4.5. Cobalt ferrite in biomedicine
A largely unexplored area about cobalt ferrite is its use in
biomedicine. Although it is known to be used as MRI contrast
agent, but in recent times, its many new facets have been
discovered. Recently, Bohara et al.222 synthesized water
dispersible amine functionalized Co0.5Zn0.5Fe2O4 nano-
particles. The authors assessed the biocompatibility of synthe-
sized samples on MCF7 cell line (human breast cancer cell line)
and found biocompatibility of upto 80 mg mL
1 concentration

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Review
of MCF7 cell line. So, these can be potential candidate in
biomedical eld such as drug delivery and hyperthermia
application.
According to Venugopalan et al.223 new biological uses of
nanoparticles can be developed. However, a major limitation is
their movement in biological systems. So authors developed
a system with cobalt ferrite, where the nanovoyager retains the
magnetic properties in various biological uids (so that its
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motion can be controlled magnetically over extended periods of
time and can generate enough thrust to propel in human
blood). A drug delivery system comprising of magnetic cobalt
ferrite nanoparticles encapsulated in SiO2 using hydroxyapatite
as template was synthesized by Pon-On et al.224 The pH
controlled release of indomethacin drug from this nano-
composite was studied. A schematic diagram representing the
drug loading and its delivery is shown in Fig. 12. It was observed
that the release of drug was signicantly faster at pH 4.0 than
at pH 7.0.
An important development in the eld of biomedicine is the
study of anti-bacterial activity of silver coated cobalt ferrites
synthesized by Kooti et al.225 The anti-bacterial activity of the
composites was investigated against Gram-positive and Gram-
negative bacteria. It was observed that the composites exhibi-
ted a greater anti-bacterial activity as compared to silver nano-
particles and some anti-bacterial drugs (penicillin, streptomycin,
cexime, amoxicillin and erythromycin). Additionally, these
composites could be magnetically removed. The anti-bacterial
activity of transition metal substituted cobalt ferrites was
Fig. 12 Conceptual picture of the preparation of CoFe2O4 nanoparticles coated with SiO2 through hydroxyapatite (HAp) as template and
controlled release of indomethacin (IMC) drug at pH 7.0 and 4.0 including demonstration of the response of magnetic SiO2-coated CoFe2O4
indomethacin (IMC) drug response to a permanent magnet (this gure has been adapted/reproduced from ref. 224 with permission from
Elsevier).
This journal is The Royal Society of Chemistry 2016
View Article Online
RSC Advances
studied by Sanpo et al.226 The substitution of zinc and copper in
cobalt ferrite nanoparticles signicantly improved antibacterial
activity against E. coli and S. aureus. Copper substituted cobalt
ferrites possessed the most eective contact biocidal property
among all nanoparticles, as shown in Fig. 13. Wu et al.227
synthesized MWCNTs/CoFe2O4 magnetic hybrids, for MRI and
drug delivery. The authors showed that anticancer drug doxo-
rubicin can be loaded into hybrids and subsequently released in
a sustained and pH-responsive way. This suggested that
MWCNT/CoFe2O4 hybrids may be used as both eective MRI
contrast agents and anticancer drug delivery systems for simul-
taneous cancer diagnosis and chemotherapy. Similary, Wang
et al.228 synthesized cobalt ferrite/graphene oxide and found it
equally eective for the same purpose. Prodelalova et al.229 re-
ported very interesting studies related to adsorption and recovery
of high molecular-mass DNA using cobalt ferrite (unmodied or
modied with a reagent containing weakly basic aminoethyl,
aminophenyl groups; and/or with alginic acid-natural carboxylic
polysaccharide). The authors observed a strong interaction
between DNA and cobalt ferrite surface, which can be attributed
to high anity of PO
(in phosphate, phosphonate, etc.) to iron
oxide. An interesting research regarding the selective removal of
ovarian cancer cells from human ascites uid using magnetic
cobalt ferrite nanoparticles was carried out by Scarberry et al.230
The authors reported that the superparamagnetic nanoparticles
conjugated with an ephrin-A1 mimetic peptide with a high
anity for the EphA2 receptor can be used to capture and remove
human cancer ovarian cells from the peritonea of experimental
RSC Adv., 2016, 6, 9769497719 | 97713

RSC Advances
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Fig. 13 Antibacterial activity against E. coli and S. aureus of synthe-
sized transition metal substituted cobalt ferrite nanoparticles (a)
without cobalt ferrite nanoparticles; (b) CoFe2O4; (c) Co0.5Cu0.5Fe2O4;
(d) Co0.5Zn0.5Fe2O4; (e) Co0.5Mn0.5Fe2O4 and (f) Co0.5Ni0.5Fe2O4 (this
gure has been adapted/reproduced from ref. 226 with permission
from Elsevier).
mice. Recently, very interesting results were reported by Park
et al.231 wherein the authors synthesized cobalt ferrite nano-
particles functionalized with hematoporphyrin (HP) and folic
acid (FA) (CoFe2O4HPsFAs). The authors observed that
CoFe2O4HPsFAs are biocompatible and non-cytotoxic and have
good MRI and remarkable anticancer activity at very low
concentration for dierent cell lines. Novotna et al.232 synthesized
silica encapsulated cobalt zinc ferrite and found them as
a perspective contrast agent suitable for cell labeling. Their use at
low non-toxic doses appeared to be safe with respect to direct
interaction between the cells and NPs. Even low doses provided
sucient contrast for MR tracking due to the higher relaxivity of
the nanocomposite.
4.6. Cobalt ferrite as sensor
Now-a-days magnetic nanoferrites are considered to be the most
promising gas sensing and electrochemical sensing materials
due to their temperature dependent surface morphology and
electronic structure respectively. The gas sensing abilities of
nanoferrites may, therefore, be increased by controlling the
surface morphology so as to increase the active surface area for
the adsorption of gas, and use of additives which act as cata-
lysts, thus promoting the improvement of the sensor properties.
Recently, Singh et al.233 investigated the liqueed petroleum gas
sensing properties of nanostructured cobalt ferrite and ferric
oxide at room temperature. The authors reported the maximum
sensitivity of cobalt ferrite lm sensor to be 2.0 MU s
1 which
was 75 times greater than that of a solid plate pellet sensor.
The response and recovery times were 30 s and 60 s respec-
tively. Similarly, Xiangfeng et al.234 investigated the gas sensing
properties of cobalt ferrite nano-crystallites synthesized via
hydrothermal route towards the sensing of ethanol. The value of
pH during the synthesis process greatly aected the type of
97714 | RSC Adv., 2016, 6, 9769497719
View Article Online
Review
response towards the gas sensing. Cobalt ferrite prepared in the
pH range 1114 exhibited p-type gas-response. However, those
prepared in pH range 810 exhibited p-type gas-response at
high temperatures and n-type gas-response at low tempera-
tures. Also, the sensor prepared at 180  C for 48 h at pH 8
showed high response and good selectivity towards ethanol at
a concentration of as low as 10 ppm. Gedam et al.235 fabricated
nickel substituted cobalt ferrite of composition Co0.8Ni0.2Fe2O4,
having average crystallite size of 30 nm. The ferrite was highly
selective towards the ammonia gas with good sensing response
at 280  C. Also, when Pd was incorporated into the system, there
was improvement in the sensor response and operating
temperature could be reduced to 280  C. Similarly, manganese
doped cobalt ferrite nanowires were utilized as humidity sensor
by Kim et al.236 Bagade and Rajpure237 synthesized cobalt ferrite
thin lms on the surface of quartz substrate. The gas sensing
measurements revealed that at 150  C operating temperature
lms showed the maximum gas sensor response of 95% for
80 ppm NO2. The response of the gas sensor increased with
increase in NO2 concentrations. The selectivity study revealed
that the cobalt ferrite thin lm based gas sensor show higher
gas response to NO2 than other test gases.
The cobalt ferrite/exfoliated graphene oxide nanohybrid was
used to modify glassy carbon electrode by Ensa et al.238 The
voltammetric investigations showed that CoFe2O4/EGO nano-
hybrid had synergetic eect towards the electro-reduction of
H2O2 and electro-oxidation of nicotinamide adenine dinucleo-
tide with detections limit of 0.38 and 0.54 mmol L
1, respec-
tively. Three ferrites of type MFe2O4 (M Fe, Co or Mn)
dispersed on multi-walled carbon nanotubes were prepared by
Zhu et al.239 Their electrocatalytic properties toward the reduc-
tion of H2O2 at pH 7.4 were systematically compared. Catalytic
reduction ability followed the order Fe3O4 > CoFe2O4 > MnFe2O4
with the limits of detection of 0.98, 2.59 and 5.64 mM.
Dimitrijevic et al.240 proposed a novel electrochemical sensor
for quantication of ascorbic acid with amperometric detection
in physiological conditions was constructed. It was observed
that introducing these nanoparticles to the surface of glassy
carbon paste electrode (GCPE) led to increasing analytical
performance. Co ferrite modied GCPE showed better charac-
teristics toward ascorbic acid sensing. The limit of detection
obtained by sensor was calculated to be 0.0270 mg L
1, with
linear range from 0.1758 to 2.6010 mg L
1.
5. Conclusions
From the entire discussion, it can be concluded that cobalt
ferrite continues to attract tremendous research interest,
because of its unique and interesting properties. Although, a lot
of work was reported on its physical and chemical properties
but the interest in this area is ever-increasing. For instances, its
properties were found to be dependent on synthetic method-
ology. This is because the method used for synthesis of cobalt
ferrite determines the particle size. Therefore, dierent
synthetic method would yield cobalt ferrite with dierent
particle sizes and hence, dierent properties. Further, in the
past decade, tremendous work has been carried out on the
This journal is The Royal Society of Chemistry 2016

Review
properties of substituted cobalt ferrites. Substitution of cobalt
or iron ions from cobalt ferrite lattice with some guest ions
results in the development of materials having entirely dierent
properties. This is an ever increasing area of research and
a continuous eort to incorporate newer ions into the cobalt
ferrite lattice is being made. A large volume of work is also re-
ported on the inuence of reaction conditions such as anneal-
ing temperature, pH, presence of additives, etc. In addition,
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various composites of cobalt ferrite have recently been synthe-
sized. These composites are shown to exhibit enhanced prop-
erties as compared to cobalt ferrite. It is therefore, not
surprising that cobalt ferrite shall continue to attract consid-
erable attention and has opened a door towards diverse
applications.
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