Journal of Saudi Chemical Society (2019) xxx, xxx–xxx

King Saud University

Journal of Saudi Chemical Society

www.ksu.edu.sa
www.sciencedirect.com

REVIEW

Review on augmentation in photocatalytic activity

of CoFe2O4 via heterojunction formation for
photocatalysis of organic pollutants in water
Sonu a, Vishal Dutta a, Sheetal Sharma a, Pankaj Raizada a,b,
Ahmad Hosseini-Bandegharaei c,d, Vinod Kumar Gupta e, Pardeep Singh a,b,*

a
School of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan, Himachal Pradesh 173212, India
b
Himalayan Centre for Excellence in Nanotechnology, Shoolini University, Solan, HP 173229, India
c
Department of Environmental Health Engineering, Faculty of Health, Sabzevar University of Medical Sciences, Sabzevar, Iran
d
Department of Engineering, Kashmar Branch, Islamic Azad University, PO Box 161, Kashmar, Iran
e
Center of Excellence for Advanced Materials Research, Faculty of Science, King Abdulaziz University, Jeddah 21589,
Saudi Arabia

Received 5 June 2019; revised 16 July 2019; accepted 17 July 2019

KEYWORDS Abstract In previous years, cobalt ferrite has gained huge consideration in the field of semiconduc-
Spinel ferrites; tor photocatalysis for waste water treatment. Cobalt ferrite and its derivatives own tunable mag-
CoFe2O4; netic properties which results in higher absorption capability in comparison with other
Heterogeneous photocatalyst semiconductors. In the current review, a brief overview of CoFe2O4 as a semiconduc-
photocatalysis; tor photocatalyst is presented and ferromagnetic behaviour of CoFe2O4 is also discussed. Few
Heterojunction formation; drawbacks such as agglomeration, photocorrosion and recombination rate of electrons-holes are
Visible light; also discussed. For the enhancement of photocatalytic action of cobalt ferrite, the role of cobalt fer-
Wastewater treatment rite with type I, type II, direct Z-scheme, solid state Z-scheme heterojunctions, Schottky and p-n
heterojunctions based on different heterostructures were also discussed. In conclusive outlook for-
mation of cobalt ferrite based heterojunctions is best approach for the enhancement of photocat-
alytic performance. This is because heterojunction formation enhanced the rate of charge

* Corresponding author at: School of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan, Himachal Pradesh 173212, India.
E-mail address: pardeepchem@gmail.com (P. Singh).
Peer review under responsibility of King Saud University.

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1319-6103 Ó 2019 King Saud University. Production and hosting by Elsevier B.V.
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Please cite this article in press as: Sonu et al., Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of
organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
2 Sonu et al.

separation and thus reduced the electron–hole recombination. Herein, this review highlights the
CoFe2O4 based heterojunctions for the photodegradation of noxious organic pollutants in water.
Furthermore, the future expectations and challenges in exploiting CoFe2O4 nanocomposites for
water treatment, also discussed in precise conclusion of this review.
Ó 2019 King Saud University. Production and hosting by Elsevier B.V. This is an open access article under
the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00

2. CoFe2O4 as a photocatalyst . . . . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
3. Synthesis methods for CoFe2O4 . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
4. Heterojunction formation as an efficient strategy to enhance photocatalytic activity of CoFe2O4 . . . . . . . . . . . . . . . . 00
5. CoFe2O4 based type-II photocatalyst . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
6. CoFe2O4 based Z-scheme photocatalyst. . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
7. CoFe2O4 based Schottky photocatalyst . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
8. CoFe2O4 based p-n heterojunction photocatalysts . ................. ............... . . . . . . . . . . . . . . . . 00
9. Elemental doping . . . . . . . . . . . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
10. Conclusive remarks . . . . . . . . . . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
Declaration of Competing Interest . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ................. ............... . . . . . . . . . . . . . . . . 00

1. Introduction A technique for oxidizing waste by hydroxyl radicals is a

All around worldwide, many problems are associated with
water pollution. Yearly, millions of people and 3900 children
die every single day from various diseases caused by drinking
polluted water and around 1.2 billion people require drinking
water security [1,2]. With the growing industrialization and
urbanization, our environment is under constant pressure of
environmental problems out of which cleanness of water is
the world’s top environmental problem [3]. In the upcoming
years, rapid population growth and urbanization will increase
day by day which results increase in the demand of pure water
for agricultural, domestic and industrial use [4]. As per W.H.O
report, by 2025, 50% of the world’s inhabitants will be living in
water stressed areas [5]. Until 2015, only around 20% of the
contaminated water was properly treated over the world. In
developing countries, without proper disposal of heavy metal
and impurities, around 70% of industrial waste water is dis-
charged [6]. Aquatic pollutants are very dangerous, and very
difficult to be cleaned up completely [7,8]. To avoid the nega-
tive effects to the environment and also on the human health,
elimination of these organic pollutants from wastewater is very
crucial [9]. The present infrastructure is not sufficient for
waste-water treatment and is also not economic [3,10]. Conse-
quently, researchers are looking for cost effective methods for
water treatment with high productivity [11] (Table 1).
In the last few years, numerous techniques have been
developed for wastewater treatment. Among them, efficient
techniques are gravity separation, micro-filtration, ultra-
filtration, solvent extraction, sedimentation, precipitation,
coagulation, flotation, oxidation, evaporation, distillation,
adsorption, electro-dialysis and electrolysis. But all these tech-
niques require high investment and are of high preparation
cost [12–34].
good option for wastewater treatment, which is known as
the advanced oxidation process [35,36]. In this technique, all
the toxic organic wastes are destroyed without transferring
into the another form, which makes it different from the other
[37]. Some of the advanced oxidation methods are as follows:
Fenton process, UV-Photolytic technique, Photo-Fenton pro-
cess, sonolysis, ozonation process, photocatalysis [38–42]. Out
of all these techniques, photocatalysis is the most favorable
technique because it uses solar energy for the mitigation of pol-
luted water [43].
In general mechanism of photocatalysis (Fig. 1), when light
falls on the surface of semiconductor photocatalyst, activation
of semiconductors takes place, and electrons in valence band
are excited to conduction band of the semiconductor and holes
will left in the valence band. The holes in the valence band can
oxidize donor molecules and react with water molecules to give
hydroxyl radicals and electrons in conduction band reacts with
oxygen species to give superoxide radicals. Indeed, the holes
are consumed in the oxidation reaction and the electrons are
used in reduction reaction. The produced reactive oxygen spe-
cies (ROS) interact with contaminants and decompose them
into less harmful materials. The photocatalytic mechanism is
explained by the following equations (Eqs. (1)–(21)) [44–46].
0
AOP s þ OH ! Pollutant
! CO2 þ H2 O þ inorganic ions ð1Þ
Photocatalyst þ ht ! e ðconduction bandÞ
þ hþ ðvalence bandÞ ð2Þ
O2 þ e ! O2 E0 0 ¼ 0:33V ð3Þ
HO2 ! O2 pKa ¼ 4:8 ð4Þ

Please cite this article in press as: Sonu et al., Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of
organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
Review on augmentation in photocatalytic activity of CoFe2O4 3

Table 1 Summary of CoFe2O4 based heterojunction photocatalysts for the elimination of pollutants present in wastewater.
Photocatalyst Method of Type of Effect of CoFe2O4 Pollutants References
synthesis heterojunction
CoFe2O4/AgBr Precipitation Type II Photodegradation efficiency of MO was increased Methyl orange [87]
method
CoFe2O4/BiVO4 Hydrothermal Type II Photodegradation efficiency of MB was increased Methylene blue [88]
method
CoFe2O4/ZnS Hydrothermal Type II Completely degraded MB within 70 min with Methylene blue dye [89]
method H2O2
CuS/CoFe2O4 Hydrothermal Type II Photodegraded MB completely within 30 min Methylene blue dye [90]
method
CoFe2O4/Ag3PO4 Precipitation Type II Photodegraded MB completely within 60 min Methylene blue dye [91]
method
CoFe2O4/g-C3N4 Calcination Type II 97.0% of MB was photodegraded Methylene blue dye [92]
method
Au-CoFe2O4/ Sol-gel method Solid Z- Photodegradation efficiency of MO was increased Methyl orange dye [93]
MoS2 scheme
BiOBr/ Hydrothermal Solid Z- Photodegradation efficiency of RhB was increased Rhodamine B dye [94]
CoFe2O4/graphene method scheme
Ag/AgBr/ Solvothermal Solid Z- Photodegradation efficiency of 4-chlorophenol 4-chlorophenol dye [95]
CoFe2O4 method scheme dye was increased
CoFe2O4/g-C3N4 Hydrothermal Direct Z- 2/1 wt ratio of CoFe2O4/C3N4 completely Rhodamine B dye [96]
method scheme photodegraded the RhB dye
MoS2/CoFe2O4 Hydrothermal Direct Z- Photodegradation of RhB and CR was increased Rhodamine B dye [97]
method scheme and Congo red dye
rGO-CoFe2O4 Hydrothermal Schottky Completely photodegraded malachite green dye Malachite green dye [98]
method junction within 15 min
CoFe2O4/graphene Hydrothermal Schottky Photodegradation of MB was increased Methylene blue [99]
method junction
CoFe2O4–RGO Co- Schottky Photodegradation of MO was increased Methyl orange [100]
precipitation junction
method
CoFe2O4/ZnO Hydrothermal p-n junction Photodegradation of MB was increased and no Methylene blue [101]
method loss in photodegradation after three cycles
CoFe2O4/ZnO Co- p-n junction Mineralization of DB71 was increased Direct Blue 71 [102]
precipitation
method

Fig. 1 Schematic design of spinel ferrite photocatalytic mechanism.

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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
4 Sonu et al.

H2 O2 þ O 
2 ! OH þ O2 þ OH

ð17Þ

3O2 ! Photocatalyst intersystem crossing!1 O2 ð18Þ

ROS; hþ þ contaminants ! oxidised productsðH2 O; CO2 Þ

ð19Þ

O2 þ pollutants þ ht ! H2 O; CO2 ð20Þ

Recombination of e- - h+ pairs [47–51]:
e þ hþ ! Heat þ radiation less decay ð21Þ
From the last few years, this technology has generated an
abundant interest for reduction of toxic compounds from the
contaminated water [52,53]. For the abatement of contami-
nated substances, many technologies have been used, which
Fig. 2 Schematic of a representative CoFe2O4 structure, show- are involved in transferring compounds between phases or
ing oxygen atoms (sky blue), Fe+3 tetrahedral (green), Fe+3/Co+2 the sources to analyze [54,55]. Spinel ferrites are best choice
octahedral (red) units (Permission taken from Elsevier, license no. for the wastewater treatment as they are nano-sized and pos-
4583591482760). sess high surface to volume ratio and super magnetic proper-
ties. Spinel ferrites have a common chemical formula AB2O4,
where A and B are metallic cations which are situated at two
O2 þ 2Hþ þ e ! H2 O2 E0 0 ¼ 0:89V ð5Þ different positions, tetrahedral (A sites) and octahedral (B
sites) and main constituent in their structure is Fe (III). Oxy-
H2 O2 ! HO
2 þH
þ
pKa ¼ 11:7 ð6Þ gen atoms are coordinated to cations of both positions tetrahe-
dral and octahedral respectively (Fig. 2) [55]. In the last few
O2 þ 2Hþ þ 2e ! H2 O2 E0 0 ¼ 0:28V ð7Þ years, scientists have focused on the synthesis of spinel ferrites,
with improved magnetic, optical, biological and catalytic prop-
H2 O2 þ e ! OH þ OH E0 0 ¼ 0:38V ð8Þ erties [56–67]. In previous years, for environmental applica-
tion, mainly for the deduction of toxic pollutants in water
H2 O þ hþ ! OH þ Hþ E0 0 ¼ 2:32V ð9Þ interest has been increased with the utilization of spinel ferrites
and their composites. The structure of spinel ferrite used as an
OH ! O
2 þH
þ
pKa ¼ 11:8 ð10Þ adsorbent to treat noxious contaminants present in the water.
They have unique physicochemical properties different from
2HO2 1 O2 ! H2 O2 ð11Þ their bulk counterparts, so these are broadly considered as
þ
adsorbents [55]. Spinal ferrite in wastewater treatment can cer-
O 1 0
2 þ h ! O2 E0 ¼ 0:65V ð12Þ tify long-lasting performance with exceptional features, such as
adjustable size, versatile surface, superior surface-volume ratio
2HO2 ! H2 O2 þ O2 ð13Þ and greatest magnetic property [68]. They can be prepared
from industrial wastes which is a cheaper method and an
2HO2 þ O
2 þ H2 O ! H2 O2 þ O2 þ OH

ð14Þ advantage for the commercial applications (Fig. 3) [55,69].
In order to examine previous works and trends of
2HO2 ! H2 O2 ð15Þ
researches on CoFe2O4 based heterojunctions for photocataly-
sis and for efficient photodegradation of organic pollutants, a
H2 O2 þ htðUVÞ ! 2OH ð16Þ

Fig. 3 Band gap positioning of spinel ferrites in interaction with aqueous solution referenced with NHE (right pH ¼ 14 and left pH ¼ 0)
relative to the standard potentials for the reduction and oxidation of water.

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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
Review on augmentation in photocatalytic activity of CoFe2O4 5

Fig. 4 (a) Number of Publications per year on ferrites from 2009 to 2019 (May), (b) Published research papers on spinel ferrites (c)
Published research papers on cobalt ferrite from 2010 to May 2019 (data taken from ‘Scopus’ using keyword nickel ferrite, magnesium
ferrite, calcium ferrite, copper ferrite, zinc ferrite, cobalt ferrite).

techniques, characteristics and favorable applications of the

CoFe2O4 based heterojunctions [53–60]. In this review, we
have considered the use of CoFe2O4 based heterojunctions
for efficient degradation of various pollutants, and modifica-
tion of CoFe2O4 for photocatalytic energy application.

2. CoFe2O4 as a photocatalyst

CoFe2O4 is an iron-based semiconductor oxide which com-

Fig. 5 Schematic design of CoFe2O4 photocatalytic mechanism
under visible light with band gap.
bibliometric study has been conceded out using search engine
‘Scopus’. On the basis of Scopus data, 1261 articles were pub-
lished in the last ten years i.e. from 2009 to 2019 (May) and, on
average, 126 papers have been reported per year (Fig. 4). The
maximum research articles are published in Separation and
Purification Technology, Chemical Engineering Journal, Ara-
bian Journal of Chemistry due to their importance to chosen
topic. Most of the research articles are focused on preparation
prises high cubic magneto crystalline anisotropy, high chemi-
cal stability, low toxicity, high coercivity, moderate
magnetization etc. [70–73]. Spinel CoFe2O4 is a ferrimagnetic
material having general formula Co2+(Fe3+)2O4, a face cen-
tered cubic (fcc) structure and large unit cell with eight for-
mula units. In the structure of spinel CoFe2O4, cations are
distributed in two types of lattices, i.e. normal spinel structure
and inverse spinel structure. In the normal spinel structure,
Co2+ have tetrahedral coordination and Fe3+ have octahedral
coordination whereas, in inverse spinel structure, Fe3+ possess
tetrahedral coordinated sites and (Co2+) and (Fe3+) equally
goes on octahedral coordinated sites [74,75]. The magnetic
properties of both normal and inverse spinel CoFe2O4 are dif-
ferent from each other, but possess same chemical composition
[66]. CoFe2O4 acts as ferrimagnetic below the Curie tempera-
ture, TC = 860 K; through neutron diffraction data a collinear
magnetic structure was obtained [76]. According to the Neel’s
ferromagnetism for two-sub lattice structure, magnetic

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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
6 Sonu et al.
moment of ions are associated antiparallel to each other at
octahedral and tetrahedral sites [77]. Saturation magnetization
increases for CoFe2O4 when temperature decreases from room
temperature to 10 K. This may happened because of spin dis-
order and reduced thermal fluctuation at the surface of
nanoparticles [78,79].
In photocatalytic reactions of CoFe2O4 based heterojunc-
tions upon light illumination and activation of semiconduc-
tors, photon’s energy is more than the photocatalyst band
gap energy, then photogenerated electron is transmitted to
conduction band from valence band and holes are generated
in valence band (Fig. 5) [80]. The generated electron-hole pairs
imitate reduction and oxidation reactions on photocatalyst
surface, generating oxidative species like hydroxide and super-
oxide radicals. CoFe2O4 is a n-type semiconductor, possess a
band gap of 1.76 eV. The reduction potential of CoFe2O4 is
0.14 eV and the oxidation potential is 1.9 eV with respect to
NHE [81]. Devi et al. fabricated rGO-CoFe2O4 through a
novel hydrothermal process for the photocatalytic degradation
of 4-chlorophenol under visible light illumination [82]. The
energy band gaps of CoFe2O4, reduced graphene oxide and
rGO-CoFe2O4 was around 2.5, 3.2 and 2.1 eV. RGO-
CoFe2O4 degraded 4-chlorophenol solution completely,
whereas bare RGO and CoFe2O4 degraded 50% and 73% of
4-chlorophenol solution, respectively. Du et al. fabricated
novel magnetic CoFe2O4 particles modified on titanate nano-
tubes (CoFe2O4/TNTs) through impregnation-calcination
method [83]. CoFe2O4/TNTs are used for phenol photodegra-
dation under visible light radiation. The synthesized photocat-
alyst exhibited 83.9% phenol photodegradation proficiency
with 0.0300 min1 kinetic rate constant as well as TOC
removal. The as-fabricated CoFe2O4/TNTs enhanced the pho-
todegradation efficiency up to 97.2% where k = 0.0607 min1,
TOC removal was 81.3% and showed 81.3% of cobalt leach-
ing which was comparatively less than that of CoFe2O4
nanoparticles. Wu and co-workers synthesized spinel magnetic
CoFe2O4-polyethylene glycol (PEG/CFO) by facile and
hydrothermal method for the removal of methyl orange,
methyl blue and congo red dye [84]. The synthesized magnetic
adsorbent CoFe2O4 catalyst showed the absorbance value
using UV–vis spectrophotometer for congo red, methyl blue
and methyl orange at 497 nm, 464 nm and 664 nm, respec-
tively. The PEG addition effected the adsorption performance
of CoFe2O4 for congo red, methyl blue and methyl orange.
With addition of PEG, the adsorption capacity for congo
red was increased and for methyl orange and methyl blue it
was decreased. PEG/CFO nanocomposite adsorbed congo
red, but cannot adsorbed methyl orange and methyl blue
and when the PEG concentration was increased the adsorption
capability increased too.
It is challenging to design and synthesize CoFe2O4 photo-
catalyst having band structure which absorb an extensive
range of visible light and also hold high redox potential and
good stability. It shows toxic effects, such as, a study showed
toxicity of CoFe2O4 nanoparticles in Zebra fish (danio rerio)
embryos. CoFe2O4 as a photocatalyst shows many limitations
such as (i) leaching, when Co2+ and Fe3+ particles are at
lower concentration, they show leaching; (ii) Agglomeration,
when Co2+ and Fe3+ particle are at higher concentration, they
show agglomeration; (iii) In strong acidic and alkaline condi-
tions their photocatalytic efficiency decreases; (iv) CoFe2O4
at pure state show high rate of electrons and holes
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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
recombination which effects the photocatalytic activity; (v)
CoFe2O4 show high rate of photocorrosion when exposed to
contamination [55,85–87]. Nowadays, researchers have
focused on CoFe2O4 to enhance the photocatalytic perfor-
mance and to eliminate the obstacles for pure CoFe2O4.
3. Synthesis methods for CoFe2O4
Due to technological importance, and fascinating magnetic
properties, synthesis of cobalt ferrite nanoparticle is becoming
one of the most interesting research area. To find out the best
synthesis methods, still more research is required even with
the progress of research in cobalt ferrite nanoparticles, which
can produce ferrite nanoparticles with high quality, in terms
of purity, shape, size, stability and morphology of the particles
[89]. There are only two categories to which synthesis methods
for nanomaterial are divided, i.e. ‘bottom-up’ and ‘top-down’.
During ‘bottom-up’ particles are formed when ions chemically
combine together, while in ‘top-down’ particles are formed
when chemicals are crushed to form tiny particles. In
‘bottom-up’, there are many synthesis techniques which include
co-precipitation, hydrothermal, thermal decomposition,
solvothermal, sol-gel, sonochemical, microwave-assisted,
microemulsion, flame spray pyrolysis, vapor deposition, and
polyol techniques. However, in ‘top-down’ synthesis, there is
only mechanical milling technique and pulsed laser ablation
are the most common technique [90]. From these synthesis
methods, hydrothermal, co-precipitation, and sol-gel tech-
niques are the best ones for the synthesis of cobalt ferrite. These
techniques have many advantages than other synthesis
methods, like lesser reaction time, milder reaction conditions,
more yields, improved selectivity and clean reaction [91]. Due
to utilization of different types of synthesis techniques, proper-
ties of cobalt ferrite nanoparticles are extremely affected by the
method used for their synthesis. On the other hand, types of the
synthesis techniques has some effects on the adsorption capac-
ity of the produced cobalt ferrite nanoparticles, when used for
decontamination of wastewater.
Synthesis of cobalt ferrite nanoparticles by coprecipitation
technique is the most useful, cost-effective and less time-
consuming, high mass production and frequently applied
technique to synthesize uniform sized nanoparticles [91].
Nanoparticles are in the super paramagnetic size range from
5 to 15 nm and by changing reaction condition the size can
be increased up to 40 nm. El-Shobaky et al. fabricated magnetic
cobalt ferrite (CoFe2O4) nanoparticles by wet chemical co-
precipitation technique [72]. Metal nitrates were used as precur-
sors and 4 M NaOH solution was used as precipitating agent.
The process was performed at 60–70 °C and a desired pH was
maintained. In order to check the variation in catalytic activity,
the sample was calcined at 400, 500 and 600 °C. Crystallo-
graphic analysis showed that high crystallinity was observed
at 600 °C but also showed the decrease in catalytic activity. This
may be due to the change in the concentration of active sites
present and participated in catalyzed reaction. Also, the sites
present in the outer surface layer of catalyst had played a major
role in the reaction. Thus, it can be concluded that high crys-
tallinity is not going to affect the catalytic activity, and the
important factor is the concentration of active sites.
Hydrothermal synthesis technique is performed in aqueous
medium in which divalent and trivalent (commonly ferric)
Review on augmentation in photocatalytic activity of CoFe2O4
transition metal salts are dissolved separately in the 1:2 mol
ratio respectively [92]. In hydrothermal synthesis technique,
solution is heated above 200 °C temperature under pressure
above 2000 psi in an autoclave. The heating temperature and
time are dependent on the type of target nanoparticles to be
achieved [93–95]. Tahmineh Sodaee et al. fabricated CoFe2-
xGdxO4 nanorods by a novel hydrothermal technique without
use of any surfactant [96]. In this work, metal nitrates were
used as precursors with 2 M NaOH solution. Hydrothermal
treatment was given at 100 °C. Crystallite size obtained was
from 15 to 40 nm with the increase in concentration of
Gadolinium. Magnetic properties of this material was
observed and it was found that coercive field has increased
from 590.35 Oe to 826.0 Oe and magnetic saturation was
found to decrease from 72.36 emu/g to 53.61 emu/g, with the
increase in Gd concentration. Thus it can be concluded that
magneto-crystalline anisotropy dominates over shape aniso-
tropy with increasing concentration of gadolinium.
Sol-gel synthesis method is broadly used for the spinal fer-
rites synthesis in which the metal alkoxide solution hydrolysis
and condensation polymerization reaction happen to produce
gels at the room temperature. Some of the advantages of the
sol-gel synthesis technique include some facts that are low cost,
operability under low temperature, no need of special instru-
ments and achievability of narrow particle size distribution
[97–99]. By adjusting different parameters such as sol concen-
tration, stirring rate and annealing temperature in sol-gel tech-
nique, composition, microstructure, purity and shape of
nanoparticles can be controlled [97,100]. The major limitation
of this method is that the nanoparticles produced lack purity
due to contamination from the reaction in the final product,
so to achieve the higher purity thermal treatment is required
after the synthesis. Ashour et al. synthesized metal-
substituted cobalt ferrites by sol-gel technique [101]. Nitrates
of cobalt, copper, zinc and manganese were taken as precur-
sors. Citric acid and ethylene glycol were used as reducing
agent and polymerization agent, respectively. Crystallographic
data clearly shows the formation of high crystalline nanostruc-
tures. Also, cobalt ferrite was calcined at different tempera-
tures from 400 to 700 °C. It was observed that with the
increase in temperature the crystallinity increases and the size
increases from 19 to 44 nm with the increase in temperature.
Fig. 6 (a) Schematic design of charge transfer in the type I heterojunction, (b) schematic design of charge transfer in the type II
heterojunction.
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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
7
Thus, it can be concluded that, with this method, highly crys-
talline nanocrystals have been prepared.
4. Heterojunction formation as an efficient strategy to enhance
photocatalytic activity of CoFe2O4
According to semiconductor photocatalyst, the main purpose
of the photocatalyst is to start or faster the redox reaction in
existence of irradiated semiconductor. Semiconductor photo-
catalysts are irradiated with photons whose energy must be
equal or greater than band gap energy of semiconductor cata-
lyst to complete the redox reactions. Electrons-holes recom-
bine with each other and disperse the input energy in the
form of light or heat. Through the scavengers or crystalline
defects, the recombination is frequently facilitated. So, a better
crystallinity can reduce the trapping positions and recombina-
tion sites, resulting the performance of the photo-generated
carriers will be increased for the preferred reaction. Recombi-
nation cannot be allowed for better photo-catalytic perfor-
mance. To increase the photocatalytic efficiency, a method is
applied in which a semiconductor heterojunction is prepared
with a secondary semiconductor [102]. When different semi-
conductors combine together between two sections with differ-
ent band structure, and generate interfacial band arrangement
is known as heterojunction.
CoFe2O4 and other metal oxide based hetero-structure pho-
tocatalyst involves combination of both CoFe2O4 and other
metal oxide, have improved photocatalytic efficiency than bare
CoFe2O4. Mostly, preparing a proper heterojunction between
CoFe2O4 and metal oxide is considered as a better scheme to
decrease electron-hole pairs recombination and to attain the
improved photocatalytic efficiency. According to diverse
charge carries separation mechanisms several semiconductor
heterojunctions can be prepared between CoFe2O4 and the
metal oxide. CoFe2O4 and metal oxide photocatalysts hetero-
junction can be categorized in the following types: (i) Type I
heterojunction, (ii) Type II heterojunction, (iii) p-n heterojunc-
tion, (iv) Schottky junction and (v) Z-scheme heterojunction.
The five heterojunction systems are discussed are the modern
developments [103].
In type I heterojunction, the semiconductor 1 has lower
valence band and conduction band higher than semiconductor
8 Sonu et al.

Fig. 7 Schematic illustration showing the electron–hole pair separation in the (a) p–n heterojunction, (b) Schottky heterojunction,
(c) solid Z-scheme heterojunction, (d) direct Z-scheme heterojunction.

2 (Fig. 6a). So, photogenerated holes in the valence band of
semiconductor 1 are transferred to valence band of semicon-
ductor 2 under visible light, while photogenerated electrons
are transferred from the conduction band of 1 semiconductor
to conduction band of 2 semiconductors. In this heterojunc-
tion there is no progress in the charge carrier separation
because all the charge carriers are stored on semiconductor 2.
In type II heterojunction, semiconductor 1 has valence
band and conduction band lower than the semiconductor 2
(Fig. 6b). So, photogenerated holes in the valence band of
semiconductor 1 can migrate to the valence band of the semi-
conductor 2 and the photogenerated electron of semiconductor
2 transferred to the conduction band of the semiconductor 1
[104]. Finally, better lifetime of the electrons and the recombi-
nation of electron-hole pairs can be reduced and the spatial.
Type II heterojunction provides finest band gap and spatial
separation of charge carriers (Fig. 6).
In p-n heterojunction, p and n type semiconductor combi-
nes and prepare a p-n heterojunction photocatalyst (Fig. 7a).
The Fermi levels of p and n type semiconductors are found
near to the conduction and valence band respectively. Holes
of p-type semiconductor will be transferred to the n-type
semiconductor by leaving negative on the p-type semiconduc-
tor. Once the Fermi level system reaches to equilibrium the
electron-hole pairs diffusion will stop. Between p and n-
type semiconductor an electric field is generated at the inter-
face and the photogenerated electron-hole pairs could be
effectively separated under the effect of electric field. So, in
the p-n junction the recombination of charge carriers will
be reduced. Type II heterojunction is not enough to over-
come recombination on semiconductor so the p-n heterojunc-
tion prepared.
In Schottky heterojunction, a metal-like material and a
semiconductor combine, they are useful in creating a
space-charge separation area. At interface of two components
electrons transfer from one to another component. So, the
recombination of charge carriers is controlled and Fermi
energy levels can be associated to increase photo-catalytic
efficiency (Fig. 7b).
In Z-scheme heterojunction, redox mediators are used
which maintain the high and strong redox abilities [105].
Application of Z-scheme heterojunction are limited to liquid
phase. So, to construct all solid-state Z-scheme photocatalytic
heterojunction a conductive solid material is used as an elec-
tron mediator. Photogenerated electrons are directly trans-
ferred from lower conduction band of semiconductor 1 to
valence band of semiconductor 2, this type of heterojunction
is known as direct Z-scheme heterojunction. Many Z-scheme
heterojunctions which have an electron mediator but direct
Z-scheme doesn’t have electron mediator. All-solid-state Z-
scheme heterojunction are generally used in gas-solid and
liquid-solid system. Metals are used as electron mediator for
fabricating Z-scheme heterojunction because they are good
conductor of electricity (Fig. 7c, d) [103].

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Review on augmentation in photocatalytic activity of CoFe2O4 9

Fig. 8 (a) Schematic illustration of photogenerated electrons and holes within CoFe2O4/AgBr nanocomposite under visible light
irradiation, (b) Schematic illustration of photocatalytic mechanism for degradation of methylene blue over CoFe2O4/BiVO4
nanocomposite under visible light irradiation (Permission taken from Elsevier, license no. 4583010779247, 4583540659402).

5. CoFe2O4 based type-II photocatalyst
Out of all investigated heterojunction systems, Type II has
exceptional staggered band structures between two photocata-
lysts, which may considerably encourage spatial parting of
holes and electrons to hinder their recombination.
Ge et al. synthesized the magnetic CoFe2O4/AgBr
nanocomposite via facile precipitation-deposition technique
for enhancement of photo-catalytic performance for pho-
todegradation of dyes (Fig. 8a) [106]. Degradation of MO by
CoFe2O4, AgBr and 20% CoFe2O4/AgBr is insignificant
without visible light radiation. The degradation of MO by
CoFe2O4 and AgBr was negligible and 89% respectively under
visible light irradiation for 60 min. Degradation efficiency was
enhanced when content of CoFe2O4 was increased in
CoFe2O4/AgBr. The degradation of MO below visible light
for 60 min by 5% CoFe2O4/AgBr, 10% CoFe2O4/AgBr, and
20% CoFe2O4/AgBr was 87%, 92% and 95% respectively.
When the concentration of MO and pH of MO was increased
the photodegradation efficiency of MO was decreased.
CoFe2O4/AgBr showed type II heterojunction in which
photoexcited electrons were transferred from CB of CoFe2O4
to CB of AgBr and holes are transferred from VB of
AgBr to VB of CoFe2O4 under visible light radiation. 20%
CoFe2O4/AgBr nanocomposite showed 16.7 emu g1
saturation magnetization (Ms), so it was easily recovered due
to magnetic properties. Hence, this photo-catalytic system is
effective for practical application under visible light.
Wetchakun et al. fabricated novel CoFe2O4/BiVO4 com-
posites by the simple hydrothermal process for photodegrada-
tion of methylene blue (MB) (Fig. 8b) [107]. Photodegradation
of MB under visible light illumination by pure CoFe2O4 and
pure BiVO4 was 8.09 ± 0.03% and 29.74 ± 0.09% respec-
tively. Degradation of MB by CoFe2O4:BiVO4 nanocompos-
ites at different mole ratios of 0.8:0.2, 0.6:0.4, 0.5:0.5, 0.4:0.6,
0.2:0.8 were at 9.27 ± 0.03%, 29.64 ± 0.09%, 27.64
± 0.09%, 45.17 ± 0.14% and 72.47 ± 0.23% respectively.
By frequent experiments the achieved standard deviation
values are symbolised by error bars. Highest photocatalytic
degradation of MB was 72.47% at the mole ratio 0.2:0.8 of
the CoFe2O4 to BiVO4 sample. Degradation of MB was
affected by the mole ratio of CoFe2O4 to BiVO4 in the
CoFe2O4/BiVO4 nanocomposite under visible light radiation.
CoFe2O4/BiVO4 displayed type II heterojunction in which
photoinduced electrons were transferred from CB of CoFe2O4
to CB of BiVO4 and the holes were transferred from VB of
BiVO4 to VB of CoFe2O4 under visible light illumination.
The photocatalytic efficacy was increased because
CoFe2O4/BiVO4 nanocomposite decreased the recombination
of electron-hole separation and the formation of hydroxyl rad-
icals. After five cycles the mole ratio 0.2:0.8 of the CoFe2O4 to
BiVO4 in CoFe2O4/BiVO4 nanocomposite have an excellent
recyclability without any decrease in photodegradation effi-
ciency. So, the fabricated CoFe2O4/BiVO4 nanocomposite
was effective for waste water treatment Fig. 8.
Farhadi and co-workers fabricated magnetic CoFe2O4/ZnS
core-shell composite with crystallite size of 18 nm by
hydrothermal method for the degradation of methylene blue,
methyl orange and rhodamine B in presence of H2O2
(Fig. 9a) [108]. The degradation efficiency of MB with
CoFe2O4/ZnS was around 51% within 70 min. and with
hydrogen peroxide, peroxydisulfate and potassium periodate
within 70 min, 50 min and 40 min, respectively was around
100%. The photocatalytic efficiency for degradation of MB
was increased due to increase in –OH radical which are gener-
ated by the addition of H2O2. Photodegradation of RhB dye
and MO dye by CoFe2O4/ZnS with H2O2 was reached around
74% and 44%. CoFe2O4/ZnS core-shell nanocomposite
showed type II heterojunction in which photoexcited electrons
were transferred from CB of ZnS to CB of CoFe2O4 and holes
were transferred from VB of CoFe2O4 to VB of ZnS under vis-
ible light irradiation. CoFe2O4/ZnS core-shell nanocomposite
reduced the recombination of electron-hole separation.
CoFe2O4/ZnS nanocomposites showed 20.2 emu g1
saturation magnetization (Ms) and ferrimagnetic behavior so,
they were easily separated from aqueous solution. For

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10 Sonu et al.

Fig. 9 Schematic design of photogenerated electrons and holes separation on the interface of (a) CoFe2O4/ZnS composite under
ultrasonic irradiation, (b) CoFe2O4/CuS nano-hybrid under ultrasonic irradiation, Schematic design of the photodegradation mechanism
of (c) CoFe2O4/Ag3PO4 and (d) g-C3N4/CoFe2O4 (Permission taken from Elsevier, license no. 4583540827055, 4583540984787,
4583541118648 and 4584711177118).

photodegradation of organic pollutants this heterogeneous
photocatalyst shows best results.
Magnetic CuS/CoFe2O4 nanohybrid was prepared by Far-
hadi et al via hydrothermal process for the photodegradation
of dyes such as methylene blue, rhodamine B and methyl
orange in presence of H2O2 (Fig. 9b) [109]. The photodegrada-
tion of MB within 30 min by H2O2, CuS/H2O2 and CFO/H2O2
was around 6%, 62%, 23% and 100%, respectively. MB com-
pletely degraded within 30 min by CuS/CFO/H2O2 under vis-
ible light radiation. Photodegradation efficiency of RhB and
MO was reached around 83% and 72% respectively by
CuS/CFO/H2O2. Increased in the concentration of
dye decrease the photodegradation around 100% to 56%.
CuS/CFO nanohybrid showed type II heterojunction in which
photoinduced electrons were transferred from CB of CuS to
CB of CFO and the holes were transferred from VB of CFO
to VB of CuS under visible light. Photocatalytic efficacy was
increased due to the generation of OH radicals which are gen-
erated by H2O2 and reduced recombination of electron-hole
separation. CuS/CFO nanohybrids saturation magnetization
was 37 emu g1 and it showed ferrimagnetic behavior.
CuS/CFO nanohybrid are easily separable from aqueous solu-
tion because of suitable ferrimagnetic behavior they are easily
recyclable after four consecutive runs.
Gan et al. fabricated core-shell CoFe2O4 incorporated
Ag3PO4 composites by the precipitation technique for degra-
dation of MB and RhB under a tungsten halogen lamp with
500 W (Fig. 9c) [110]. Ag3PO4-CoFe2O4 nanocomposite type
II heterojunction suppress the recombination electron-holes
charge carries. Ag3PO4-CoFe2O4 nanocomposite shows
better photo-catalytic efficiency than Ag3PO4 because
Ag3PO4-CoFe2O4 nanocomposite degrade MB and RhB dye
completely within 30 min under tungsten halogen lamp. When
the concentration of CoFe2O4 was increased it might
have decreased the degradation speed. Such as when the
Ag3PO4-CoFe2O4–7.5% showed better degradation speed than
Ag3PO4-CoFe2O4–10%, this gives the negative effect for the
photo-catalytic efficiency of the Ag3PO4-CoFe2O4–10%. When
the dye concentration was increased Ag3PO4-CoFe2O4 com-
pletely degrade the dye within 60 min. Ag3PO4-CoFe2O4
nanocomposite type II heterojunction in which photoexcited
electrons were transferred from CB of Ag3PO4 to CB of
CoFe2O4 and holes were transferred from VB of CoFe2O4 to
VB of Ag3PO4 under visible light radiation. The photocatalytic
efficiency was increased due to the reduced recombination of
electron-hole pairs and formation OH radicals. The presence
of CoFe2O4 increased the photocatalytic efficiency and reduced
the band of Ag3PO4. The synthesized Ag3PO4-CoFe2O4
nanocomposites were easily separable from the aqueous
solution due to ferromagnetic properties of CoFe2O4.
CoFe2O4/g-C3N4 nanocomposite was fabricated by Huang
et al. through the novel calcination method for the removal
MB under light illumination. Photodegradation of MB with-
out any photocatalyst was negligible under visible light
(Fig. 9d) [111]. MB was slightly degraded by H2O2 under vis-
ible light. It was also reported that pure CoFe2O4 did not show
any photocatalytic activity whereas CoFe2O4 photodegraded
around 40.1% of MB in 3 h when 0.5 ml H2O2 was added.
Mass ratio of CoFe2O4 in CoFe2O4/g-C3N4 nanocomposites
significantly affected the photo-catalytic efficiency. When the

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Review on augmentation in photocatalytic activity of CoFe2O4
Fig. 10 (a) Schematic design of solid Z-scheme electron transfer in Au-CoFe2O4/MoS2 (b) schematic design of photocatalytic process for
Ag/AgBr@CoFe2O4 nanocomposite under visible light irradiation (Permission taken from Elsevier, license no. 4583561013352 and Royal
Society of Chemistry).
mass ration of CoFe2O4 was 41.4% and 25.3% it degraded
97.3% and 84.6% respectively of MB dye within 3 h under-
neath visible light irradiation, so the mass ratio of CoFe2O4
was 41.4% showed better photocatalytic activity. When the
mass ratio of CoFe2O4 was 64.7% it degraded 51.5% of MB
within 3 h under visible light irradiation. So that, when the
mass ratio of CoFe2O4 was further increased more than
41.4% in CoFe2O4/g-C3N4 nanocomposites it slightly
decreased the photo-catalytic efficiency. So the proper concen-
tration of CoFe2O4 in composite is important to improve the
photo-catalytic activity. CoFe2O4/g-C3N4 nanocomposites
showed type II heterojunction in which photoinduced elec-
trons were transferred from CB of g-C3N4 to CB of CoFe2O4
and the holes were transferred from VB of CoFe2O4 to VB of
g-C3N4 under visible light. The photocatalytic efficiency was
increased due to formation of OH radicals by H2O2
and the reduced recombination of electron-hole separation.
CoFe2O4/g-C3N4 nanocomposites showed 76.6 emu g1 satu-
ration magnetization. This heterojunction was easily separable
from the aqueous solution due to ferromagnetic properties of
CoFe2O4. CoFe2O4/g-C3N4 showed 97.0% degradation of
MB in visible light after three consecutive cycles.
6. CoFe2O4 based Z-scheme photocatalyst
Though all the aforementioned heterojunctions can attain
improvement in separation competence of electron-hole, the
redox capability of composite is negotiated because of the fact
that reduction and oxidation occur on semiconductor with less
reduction and oxidation potentials, respectively. In order to
diminish these limitations, the innovative work of fabricating
a Z-scheme system was propositioned. Nonetheless by using
redox intermediaries, applications of Z-scheme systems are
restricted to liquid phase. Associated with liquid-phase
Z-scheme, all-solid-state Z-scheme systems can be more exten-
sively used in both gas-solid and liquid-solid systems.
Liu et al. fabricated a unique magnetic Au-CoFe2O4/MoS2
nanocomposite via sol-gel process for the photocatalytic
degradation of MO dye in visible light radiation (Fig. 10a)
[112]. Au-CoFe2O4/MoS2 nanocomposites showed solid
Z-scheme photocatalysis in which Au nanoparticles are at
interface of CoFe2O4 and MoS2 increased the electron-hole
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organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
11
separation through solid Z-scheme transfer mechanism.
Photodegradation of MO without any composite can be
ignored under visible light irradiation. Better photodegrada-
tion efficiency observed from Au-MoS2 or AuCoFe2O4 than
MoS2 or CoFe2O4 nanoparticles it was due to Au nanoparti-
cles, due to great conductivity enhance fast charge transfer
from CoFe2O4 or MoS2. CoFe2O4 and Au-CoFe2O4 showed
less photodegradation efficiency than MoS2 and Au-MoS2.
Generally Au-CoFe2O4/MoS2 nanocomposite showed best
photodegradation efficiency under visible light irradiation
within 120 min. Au-CoFe2O4/MoS2 nanocomposite showed
60% more photodegradation than CoFe2O4/MoS2, this indi-
cates that Au nanoparticles have increased the charge transfer
over the interface and Au acted as an electron transfer media-
tor. Photocatalytic efficiency was enhanced due to formation
of O–2 and decreased recombination of electron-hole separa-
tion. Finally, magnetization CoFe2O4 at room temperature,
high conductivity of Au nanoparticles and large surface area
of MoS2 are combined together for the highly ferrimagnetic
recollect able photocatalyst for the photodegradation of pollu-
tants below visible light.
Li et al. fabricated BiOBr/CoFe2O4/graphene nanocompos-
ite via novel hydrothermal technique which was based on
simple Z-scheme photocatalyst for the removal of RhB under
visible light radiation [113]. Pure BiOBr photodegrade RhB
dye completely within 90 min. under visible light
irradiation. CoFe2O4 increase the photodegradation rate
BiOBr because when two components forms a heterojunction,
the photoexcited electrons transfers and stabilizes effectively.
When the concentration of CoFe2O4 increased more
than 15 wt%, the photocatalytic efficiency was decreased.
BiOBr/CoFe2O4-10 wt% was used to prepare Z-scheme
nanocomposite and it showed best photocatalytic efficiency.
A ternary nanocomposite BiOBr/CoFe2O4/G showed
better photodegradation of RhB dye than BiOBr/CoFe2O4.
When the concentration of graphene was increased in
BiOBr/CoFe2O4/G from 0.5 wt% to 2.0 wt%, the photodegra-
dation of RhB increased firstly than decreased conversely and
the highest photodegradation of RhB was showed by
BiOBr/CoFe2O4/G when the concentration of graphene was
1.0 wt%. Ternary nanocomposite BiOBr/CoFe2O4/G showed
better photocatalytic activity than BiOBr/CoFe2O4 binary
12 Sonu et al.

Fig. 11 (a) Schematic design of hole-electron separation transfer process for CoFe2O4/g-C3N4 catalyst in the presence of H2O2 under
visible light irradiation, (b) Schematic design of direct Z-scheme mechanism between MoS2 and CoFe2O4 (Permission taken from Springer
nature, license no. 4583571388276 and permission taken from Elsevier, license no. 4583580286398).

composites. In ternary nanocomposite graphene acted as an photocatalysis in which photoexcited electrons in CB of

electron transfer mediator which enhance the photocatalytic
efficiency. Photocatalytic efficiency was increased due to the
formation of OH, O–2, hole and electron, respectively. The
ternary nanocomposite was easily separable due to magnetic
properties.
Xu et al. synthesized Z-scheme magnetic Ag/AgBr/
CoFe2O4 by solvothermal technique for the photodegradation
of 4-chlorophenol dye (Fig. 10b) [114]. Photodegradation of 4-
chlorophenol without any catalyst was negligible under visible
light irradiation, it showed that the 4-chlorophenol was chem-
ically stable. Photodegradation of 4-chlorophenol in presence
of Ag/AgBr and 15% Ag/AgBr/CoFe2O4 was 30.5% and
83.6% respectively under visible light irradiation within
140 min. Ag/AgBr/CoFe2O4 showed solid Z-scheme photo-
catalysis in which photoinduced electrons were transferred
from CB of AgBr to metallic Ag and quenched with the holes
which are coming from VB of CoFe2O4. Ag acted as an elec-
tron transfer mediator in Ag/AgBr/CoFe2O4 which enhance
the photocatalytic efficiency. Photodegradation efficiency was
increased due to formation of O–2, OH and reduced recom-
bination of electron-hole separation. 15% Ag/AgBr/CoFe2O4
showed better photo-catalytic degradation than Ag/AgBr.
15% Ag/AgBr/CoFe2O4 saturation magnetization 5.5 emu/g
and showed ferrimagnetic behavior so, it was easily separable
from aqueous solution due to its magnetic properties.
CoFe2O4/g-C3N4 hybrid of direct Z-scheme was synthe-
sized by Yao et al. through a simple hydrothermal technique
for removal of dyes under natural light (Fig. 11a) [115]. The
degradation of RhB without any photocatalyst can be ignored
and with H2O2 the degradation of RhB is around 3.2% under
light irradiation. Photodegradation of RhB by g-C3N4 was
weak and by CoFe2O4 69% of RhB was destroyed in presence
of H2O2 within 210 min. When the concentration of CoFe2O4
was increased the photo-catalytic efficiency was also increased
and at the weight ratio 2/1 of CoFe2O4/C3N4 it degraded
100% of RhB dye within 210 min under indoor natural
light irradiation. CoFe2O4/C3N4 (2:1) showed better
photo-catalytic efficiency than g-C3N4 and CoFe2O4.
CoFe2O4/g-C3N4 hybrid showed direct Z-scheme
CoFe2O4 were transferred and recombined with the holes in
the VB of g-C3N4. So, the CoFe2O4/C3N4 heterojunction
enhance the photo-catalytic efficiency because the efficient
charge separation from the interfacial contact between the
two components which suppresses the recombination of
electron-hole pairs. Photocatalytic efficiency was enhanced
due to the formation of O2 and h+. Degradation efficiency
was influenced by dye concentration, pH of primary solution
as well as amount of H2O2. CoFe2O4/C3N4 saturation magne-
tization 0.31 emu/g so they magnetically separable. Finally,
CoFe2O4/C3N4 heterojunction as direct Z-scheme was low
cost, and shows best photo-catalytic efficiency.
Zeng et al. fabricated MoS2/CoFe2O4 nanoparticles by the
novel hydrothermal process for the photodegradation organic
dyes [116]. Photodegradation of RhB and CR without any
photocatalyst was negligible under visible light illumination.
Photodegradation rate of RhB under visible light radiation
for bare MoS2 and CoFe2O4 was around 24.63% and
16.27% respectively within 90 min. Photodegradation rate of
CR by pure MoS2 and pure CoFe2O4 was around 44.60%
and 33.18% respectively within 90 min under visible light irra-
diation. MoS2/CoFe2O4 have better photocatalytic efficiency
than pure MoS2 and pure CoFe2O4, mass ration MoS2 and
CoFe2O4 have an effect on photo-catalytic efficiency in
MoS2/CoFe2O4. When the mass ratio of MoS2 and CoFe2O4
was 3:1, the photocatalytic efficiency for the degradation of
RhB was 93.80% in 90 min and degradation of CR was
94.43% within 50 min under visible light radiation. It hap-
pened because of the separation of electrons-hole pairs which
are accelerated by the heterojunction between MoS2 and
CoFe2O4. When mass ratio of CoFe2O4 and MoS2 was 1:2
the photocatalytic efficiency was decreased under visible light
radiation, the degradation of RhB was 73.61% in 90 min.
and degradation of CR was 77.71% within 50 min. The pho-
todegradation of RhB was around 48.69% in 90 min. and
degradation of CR was 67.56% when the mass ration of
CoFe2O4 and MoS2 was 1:4. MoS2/CoFe2O4 nanocomposites
showed direct Z-scheme photocatalysis in which photogener-
ated electrons in CB of CoFe2O4 were recombined with holes

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Review on augmentation in photocatalytic activity of CoFe2O4 13

in VB of MoS2. Photocatalytic efficiency was increased due to

the formation of O–2 and h+ radicals. When mass ratio of
CoFe2O4 and MoS2 was 1:3 saturation magnetization was
0.14 emu g1. After seven cycles of MoS2/CoFe2O4 nanocom-
posites show the photodegradation of RhB and CR around
82% and it is easily separable from aqueous solution due to
magnetic properties (Fig. 11b).

7. CoFe2O4 based Schottky photocatalyst

The Schottky junction comprises of metal material and semi-

conductor, which is advantageous in fabricating a space-
charge region. Magnetic rGO-CoFe2O4 hybrid nanocomposite
was prepared by He et al. through simple hydrothermal pro-
cess for the photodegradation of malachite green below visible
light [117]. Hybrid rGO-CoFe2O4 nanocomposite showed
granular morphology with average size of 17 nm. Hybrid
rGO-CoFe2O4H2O2 increased the photodegradation of mala-
chite green dye, it degraded malachite green dye completely
within 15 min under visible light. In this heterojunction the
recombination of electron-holes reduced and photocatalytic
efficiency was found increased. rGO-CoFe2O4 hybrid Fig. 13 Conclusive outlook for modified CoFe2O4 photocata-
nanocomposite showed schottky heterojunction in which pho- lysts for pollutant degradation.
toexcited electrons in the CB of CoFe2O4 were transferred to
the CB of rGO and holes in VB of rGO were help in the
formation of OH radicals which increased the photocatalytic photodegradation than pure CoFe2O4. Photodegradation of
efficiency. The photodegradation efficiency of the hybrid MB was 100% done by CoFe2O4/graphene 10 wt% within
rGO-CoFe2O4 nanocomposite was much more than the 1 h under visible light irradiation. MB was completely photode-
nanoparticles and photodegradation was increased with graded by CoFe2O4/graphene 5 wt% and CoFe2O4/graphene
increase of rGO/CoFe2O4 ratio and initial pH. rGO-CoFe2O4 20 wt% within 2 h under visible light irradiation.
hybrid nanocomposite saturation magnetization was in the CoFe2O4/graphene 40 wt% also completely degraded the MB
range 61.82–63.73 emu/g and ferromagnetic behavior so; it dye but it takes 3 h to reach the complete degradation under
was easily separable from the aqueous solution. visible light irradiation. CoFe2O4/graphene nanocomposites
Shang and co-workers synthesized magnetic showed schottky heterojunction in which photogenerated
CoFe2O4/graphene nanocomposites by a novel hydrothermal electrons in the CB of CoFe2O4 were transferred to the CB of
process for the photodegradation of methylene blue [118]. graphene and the holes in VB of CoFe2O4 helps in the
Photodegradation of MB by pure CoFe2O4 was around 34% formation of OH radicals which enhance the photocatalytic
in 2 h or more under visible light radiation. Magnetic efficiency (Fig. 12a). In this graphene acted as a charge carrier
CoFe2O4/graphene nanocomposites showed high rate of which increased the photo-catalytic efficiency of CoFe2O4.

Fig. 12 (a) Schematic design of the photocatalytic mechanism for the photodegradation of the MB dye, (b) Schematic design of the
photocatalytic mechanism of CF–RGO nanocomposites for photodegradation of dye (Permission taken from Elsevier, license no.
4583570964226 and Royal Society of Chemistry).

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14
CoFe2O4/graphene was easily separable from the aqueous solu-
tion due to magnetic properties of CoFe2O4 and reused many
time without losing photo-catalytic efficiency (Fig. 13).
Ghosh et al. synthesized CoFe2O4–RGO nanocomposite by
co-precipitation method ‘in situ’ for removal of various dyes
underneath visible light radiation [119]. Without the presence
of photocatalyst, no photocatalytic degradation was witnessed.
The nanocomposite CoFe2O4–RGO with H2O2 showed
enhancement of photocatalytic action under visible light radia-
tion. CoFe2O4–RGO nanocomposite which have 5, 10, 15 and
25 wt% RGO concentration photodegraded MO dye within
270, 150, 120 and 60 min respectively under visible light irradi-
ation. Further increased concentration of RGO has decreased
the photodegradation efficiency of MO. So, CoFe2O4–RGO
25 wt% showed upmost photocatalytic activity for the elimina-
tion of MO under visible light. CoFe2O4–RGO nanocomposite
showed schottky heterojunction in which the photoexcited elec-
trons in the CB of CoFe2O4 were transferred to the CB of RGO.
CoFe2O4–RGO nanocomposite photocatalyst reduced the
recombination of electron-hole separation and helps in the for-
mation of OH, O radicals. CoFe2O4–RGO was simply
2
removed from the aqueous solution due to magnetic properties
of CoFe2O4 and this showed same photo-catalytic activity after
4 consecutive cycles (Fig. 12b).
8. CoFe2O4 based p-n heterojunction photocatalysts
While Type II system can preferably separate charge carriers in
space, attained enhancement in electron-hole separation
throughout Type II heterojunction is not adequate to over-
awed the fast recombination of electron-hole on semiconduc-
tor. In respect of this, hypothesis of fabricating a p-n
heterojunction system is proposed frontward, which is compe-
tent to deliver an extra electric field to hasten the transfer of
electron-hole pairs for increasing photocatalytic activity. The
separation efficacy of electron-hole pairs in p-n system is
quicker than that of Type II system, which can remarkably
boost the photocatalytic action.
Mishra et al. fabricated magnetic CoFe2O4-ZnO photocat-
alyst by hydrothermal technique for the photodegradation of
methylene blue (MB) under visible light [120]. In the presence
of CoFe2O4-ZnO, absorption spectra of MB solution changed
many times under UV light. With increased UV exposure time
at 298 nm, the absorption peak drops slowly within 60 min
during the reaction and there was no absorption bands
appeared in the UV or visible regions, which showed the whole
photo-catalytic decolourization of MB solution. CoFe2O4-
ZnO photocatalyst was easily separable from aqueous solution
due to ferrimagnetic properties of CoFe2O4. CoFe2O4-ZnO
nanocomposite did not show any loss in photo-catalytic activ-
ity after the three cycles for the photodegradation of MB.
CoFe2O4-ZnO saturation magnetization was 51 emu g1 and,
because of ferromagnetic behaviour, this photocatalyst was
easily separable from aqueous solution. Thickness of ZnO shell
affected the photocatalytic efficiency, so that the thicker ZnO
shell caused a higher photo-catalytic efficiency.
A magnetic ZnO supported CoFe2O4 was fabricated
through a novel co-precipitation method by Anandan et al.
for mineralization of direct Blue 71 dye underneath visible
light [121]. CoFe2O4/ZnO showed zero decolorization of DB
71 under visible light. Decolorization efficiency for the DB71
Please cite this article in press as: Sonu et al., Review on augmentation in photocatalytic activity of CoFe2O4 via heterojunction formation for photocatalysis of
organic pollutants in water, Journal of Saudi Chemical Society (2019), https://doi.org/10.1016/j.jscs.2019.07.003
Sonu et al.
by pure ZnO was 0.62  104 s1 under visible light, when
concentration of CoFe2O4/ZnO was 1.6 g/L showed the
maximum decolorization rate 2  104 s1 under visible
light radiation. By further increased concentration of
CoFe2O4/ZnO nanocomposite, the decreased decolorization
rate under visible light irradiation was observed.
CoFe2O4/ZnO was easily separable from the aqueous solution
due to magnetic properties of CoFe2O4. The maximum rate for
photo catalytic mineralization and of DB 71 was witnessed in
the existence of CoFe2O4/ZnO and PMS catalysts because of
generation of greater number of non-selective hydroxide and
superoxide radicals and easily generated chain type reaction
during photocatalytic process.
9. Elemental doping
The metal/non-metal doping is a significant strategy for the
modification of optical band gap of any photocatalyst. As a
factor of duration of photocatalytic reaction, major fraction
of photo-generated holes and electrons lean towards recombi-
nation before getting to the surface of photocatalyst. As a
result, only partial holes and electrons reach the surface of
photocatalyst. Transition metal ions as dopants can change
host lattice defects, crystallinity, prevent recombination of
e--h+ pairs, extend the life time of charge carriers and also
extend absorption region in semiconductor photocatalyst. Sev-
eral metal ions have been used as dopants as Ho3+, N3+, Sn2+
and Zn2+ to tune the band gap of CoFe2O4 [122,123]. Metal
dopant, such as Mn3+ and Fe3+, results into a red shift in
the energy band, i.e. transition in between impurity levels to
the valence band or conduction band. These metal ions unite
within crystal lattice of semiconductor photocatalyst and con-
struct impurity levels in semiconductor forbidden band. For an
effective doped semiconductor photocatalyst two conditions
are required: (i) trapped e- and h+ can be free and drift to
the interface and (ii) dopant can capture e- and h+ to promote
local separation. Moreover, Mn3+ used as a metal dopant can
narrow band gap and also rise optical absorption for visible
light and IR regions [14]. The non-metal dopants, such as
Ni, can helps in locating extra extrinsic electronic levels in
the band gap of a semiconductor photocatalyst. Lately, vari-
ous non-metals dopants such as N, Ni, C, S, P, F and Br were
also used to tune the band gap of CoFe2O4 photocatalysts [14].
The traditional non-metal doping method depends on the
adsorption of organic ligands or gas molecules on the surface
of photocatalyst which results in small absorption peaks in UV
spectra. In this method, first step includes embedment of
dopant precursor into shallow lattice and then thermal treat-
ment was used for making a homogenous doping.
10. Conclusive remarks
Herein, this review emphasizes on the use of CoFe2O4 based
heterojunctions for the photodegradation of various organic
contaminants in wastewater. This review briefly discusses the
role of CoFe2O4 nanoparticles with type II, direct Z-scheme,
solid state Z-scheme, Schottky and p-n heterojunctions based
on different heterostructures and charge transfer. There are
some important points related to cobalt ferrite, which can be
summarised as below:
Review on augmentation in photocatalytic activity of CoFe2O4
 Their photo-catalytic performance and properties are supe-
rior due to their low band gap, fast transfer ability for
charge shippers, first-rate visible light response, morpholog-
ical structure, chemical functionalities, annealing tempera-
ture and their functional groups.
 Whereas cobalt ferrite and its composites have large poten-
tial due to low-cost, tunable properties and admirable mag-
netic properties, they show higher sorption ability as
compared with different semiconductors.
 At various stoichiometric amounts, the combination of
cobalt ferrites with other photocatalysts have revealed a
synergistic effect that produces enriched photocatalytic per-
formances. Moreover, combination of two photocatalysts
with different positions of band gap effectually results in
better separation of electron hole pairs, permitting more
of species to be accessible for reactions to degrade the pol-
lutants present in water.
 The Z-scheme heterojunction of cobalt ferrite can be a
favourable solution in increasing photocatalytic perfor-
mance, lowering their toxicity, and also preventing
agglomeration.
 Moreover, production of cobalt ferrite using industrial
wastes is under investigation still, but this type has potential
of being eco-friendly.
 Furthermost studies should be focused on the application of
cobalt ferrite nanoparticles because they are extremely reac-
tive and mobile in an aqueous medium.
Declaration of Competing Interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
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