Materials Today Energy 9 (2018) 83e113

Contents lists available at ScienceDirect

Materials Today Energy

journal homepage: www.journals.elsevier.com/materials-today-energy/

A review on recent advances in photodegradation of dyes using doped

and heterojunction based semiconductor metal sulfide nanostructures
for environmental protection
Dasari Ayodhya*, Guttena Veerabhadram
Department of Chemistry, Osmania University, Hyderabad 500007, Telangana State, India

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

Article history: Among the admired photocatalysts, metal sulphide-based semiconductors are most prominent photo-
Received 11 January 2018 catalysts for the degradation or decomposition of dyes in wastewater industries with low cost,
Received in revised form environment-friendly and sustainable treatment technologies for the environmental protection. In
20 April 2018
recent years, the environmental pollution poses a serious threat to the environment and public health. To
Accepted 9 May 2018
overcome the environmental pollution, doped and heterojunction based semiconductor metal sulfide
Available online 22 May 2018
nanostructures (MSNSs) are developed as photocatalysts for the purpose of photocatalytic degradation or
removal of large organic dyes in an eco-friendly and sustainable fashion. This comprehensive review
Keywords:
Semiconductors
starts with a brief overview on dyes as pollutants, dyes classification, dyes decolorization or degradation
Metal sulfide nanostructures strategies and focuses on the mechanisms involved in comparatively well understood MSNSs photo-
Heterojunctions catalysts such as ZnS, CdS, CuS, Ag2S, Bi2S3, CoS, FeS, and PbS etc. It particularly discusses the recent
Dopants advancements to enhance photocatalytic degradation of toxic dyes by using various MSNSs to make it a
Heterogeneous photocatalysis flexible and cost-effective commercial dye treatment technology. In addition, we have focused on the
treatment of organic dyes using different types of MSNSs by photocatalysis and the effects of various
parameters such as dopants, heterojunctions, band gap, size, light intensity, surface area, reaction time,
and degradation efficiency, etc., are highlighted.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction To these chemical reactions, the tag ‘photochemical’ was properly

In the past, worldwide efforts have been undertaken to use
sunlight for energy production, environmental protection and
water purification, in which photocatalysis plays a crucial role. The
term “photocatalysis” is a potential new method capable of elimi-
nating relatively recalcitrant organic compounds. This methodol-
ogy is based on the production of electronehole pairs by
illumination with light of suitable energy, of a semiconductor ma-
terial such as metal sulfide nanostructures dispersed in an aqueous
medium. The turning point that allowed photochemistry to become
a science on its own was recognizing the difference with that of
thermal chemistry [1]. At the beginning of the 20th century, many
scientists felt that irradiation was one of the many ways available
for catalyzing a reaction, which is making it faster, such as heating
or treating with some chemicals in a catalyzed chemical reaction.
* Corresponding author.
E-mail address: ayodhyadasari@gmail.com (D. Ayodhya).
assigned, while the term ‘photocatalytic’ designated reactions
accelerated by light, but maintaining the same course as the ther-
mal reactions. The large use of the term photocatalysis and the
development of a discipline specifically designed by this name
began in the 1970s, with reference to two different topics. First, the
oil crisis gave a strong impulse to the research of alternative energy
sources, and it was hoped that man could imitate nature by
exploiting solar energy for the generation of a fuel, in particular,
hydrogen generation by water splitting by photocatalysis [2,3]. The
second topic is concern about increased the pollution by chemicals
used and it was proposed that photocatalysis might clean up water
and air avoiding the addition of further chemicals [4]. The two
topics grew up from different traditions and remained separated.
In the 1970s, the photocatalytic treatment of water splitting to
the generation of hydrogen on semiconductor nanoparticles was
discovered. Thereafter, the development of research toward un-
derstanding the fundamental processes occurring in photocatalysis
and enhancing the photocatalytic degradation efficiency of the
process. Especially nanosized particles (1e100 nm) show high

https://doi.org/10.1016/j.mtener.2018.05.007
2468-6069/© 2018 Elsevier Ltd. All rights reserved.
84 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
potential in photocatalysis process owing to their unique physical
and chemical properties; and high surface to volume ratio [5].
Nanotechnology is interestingly considered to be one of the key
technologies of the 21st century [6] with over 1900 consumer
products that contained nanomaterials in 2017 over all technolo-
gies [7]. Nanoparticles applications are versatile and range from
industrial and environmental goods like, e.g., paints, detergents,
coatings or catalysts [8], to everyday products derived from food,
textile [9] or cosmetic industries [10]. The photocatalyst material
such as activated by light, it plays a decisive role to perform an
efficient photocatalytic reaction, and therefore its selection should
be done carefully to fulfill both, the appropriate electronic structure
and reasonable energy of light for its photoactivation as the rate of
the photocatalytic reaction is independent of the “active site” [11].
The tendency of photoactivation achieved by the unique photo-
physical and photochemical (photocatalytic) properties of these
nano-sized photocatalysts [12,13]. The photocatalytic degradation
of the toxic compounds (dyes, pesticides, phenolic compounds etc.)
using the photoactive materials in an aqueous medium is mainly
depends on the band gap, surface area, amount of catalyst, and
generation of an electronehole pair. It has been observed that the
surface area plays a major role in among all factors in the photo-
catalytic degradation of dyes, by providing a higher surface area,
which leads to the higher adsorption of dye molecule on the surface
of photocatalyst and enhances the photocatalytic activity.
As a typical and important class of photocatalysts, semi-
conductor nanostructures (MSNSs) such as metal oxides, metal
sulfides and mixed compounds etc. have attracted much attention
over the past decade due to their unique physical and chemical
properties. In the properties of MSNSs, the quantum confinement
occurs when one or more dimensions of semiconductor nano-
structures are close to or smaller than the exciton Bohr radius,
which is the limit size that a material maintains the continuous
band structure [14,15]. So the band gap of MSNSs can be delicately
tuned by simply controlling their particle sizes without altering the
chemical compositions of metal sulfide, which is the reality of bi-
nary MSNSs. Based on this, during last decades, there are a number
of novel techniques that have been developed for band gap tuning
of binary metal sulfide through simple artificial size control [16,17].
The diversity of these MSNSs allows targeting of many very
different properties and applications such as electrochemical de-
vices, energy storage devices, Na & Li-Ion batteries, biological,
catalysis, photocatalysis, high-performance supercapacitors and
sensors & transducers (colorimetric, fluorescence and electroana-
lytical techniques), etc.
In semiconductor nanostructures, the metal oxides also can act
as sensitizers for light-induced redox-processes due to the elec-
tronic structure of the metal atoms in chemical combination, which
is characterized by a filled valence band, and an empty conduction
band [18]. Upon irradiation, valence band electrons are promoted to
the conduction band leaving a hole behind. These electronehole
pairs can either recombine or can interact separately with other
molecules. The holes may react either with electron donors in the
solution or with hydroxide ions to produce powerful oxidizing
species like hydroxyl or superoxide radicals [19,20]. Apart from the
other semiconductor materials, the large numbers of semi-
conductors (metal oxides and complex oxides) such as TiO2 [21],
ZnO [22], WO3/TiO2 [23], Nd2O3 [24,25], Nd2Sn2O7 [26], Nd2Sn2O7-
SnO2 [27], Nd2Zr2O7 [28], Ag/CeO2 [29], Ho2O3-SiO2 [30], Ho2O3
[31e33], Dy2Ce2O7 [34,35], Dy2Sn2O7-SnO2 [36], CuCr2O4 [37],
Pr2Ce2O7 [38], CoOx/BiVO4 [39], Pr6O11 [40,41], ZrO2 [42],
Nd2O3eSiO2 [43], Nd2Zr2O7eZrO2 [44], Pr2Zr2O7 [45], and Cu2O/
TiO2/Bi2O3 [46] have also been tried in combination with several
oxides to serve as photocatalyst for the degradation of toxic pol-
lutants for the environmental wellbeing.
During the past decades, as a green and sustainable technology,
heterogeneous photocatalysis using semiconductors has received
much attention because of its potential to address energy and
environmental problems. Based on this heterogeneous photo-
catalysis, this comprehensive review discusses the recent de-
velopments in the synthesis and application of semiconductor
MSNSs (ZnS, CdS, CuS, Ag2S, Bi2S3, CoS, FeS and PbS etc.) as pho-
tocatalysts in the field of heterogeneous photocatalytic degradation
of various dyes by varying different parameters such as the size of
the materials, band gap, light intensity, surface area and concen-
trations of dye solutions; and their interactions with aquatic con-
taminants as well as the harmful environmental complications. It
also discusses the structure, size, and surface area of the synthe-
sized MSNSs photocatalytic nanostructured materials and applied
for the photocatalytic degradation of toxic dyes under UV, visible
and solar irradiations; and their dye degradation capabilities. The
knowledge gap and future research needs are also identified, and
the challenges in assessing the environmental fate and transport of
nanoparticles in heterogeneous systems are also discussed. This
review will help the engineers and scientists in this field to un-
derstand the latest developments on MSNSs in the field of photo-
catalytic degradation of dyes for the environmental applications.
2. Fundamental concept of dyes
2.1. Outline of dyes
A dye may be defined as a colored and toxic substance which
when applied to the fabrics imparts a permanent color and the
color is not removed by washing with water, detergents or a
revelation to light. It is colored because it absorbs light in the whole
visible range of the spectrum at a certain wavelength. They are
applied in various industries such as leather, paint, textile, printing,
paper, rubber, cosmetics, plastic, pharmaceuticals and food in-
dustries [47,48]. Furthermore, dyes can also affect the aquatic
plants as they reduce sunlight transmission through water. There-
fore, the removal of such colored compounds as dyes from waste
effluents becomes environmentally important because even a small
amount of dye in water can be toxic and highly visible [49].
Different physicochemical processes have been applied for the
treatment of colored wastewater such as removal or decolorization
and degradation of dyes. These include precipitation, flocculation,
electro-kinetic coagulation, electro-flotation, ion exchange, mem-
brane filtration, electrochemical destruction, irradiation and
ozonation. However, all these treatment methods are expensive,
suffering from many restrictions and cannot be utilized by small
industries to treat the wide range of wastewater [50]. Hence,
adsorption process has been preferred for the treatment of the
wastewater due to its stinginess, low-cost, inexpensive, simple
design and easy operation, not affected by toxic substances and
high quality of the treated effluents, particularly for well-designed
sorption processes [51,52].
2.2. Classification of dyes
The general classification of dyes and other colored substances is
based on the composition of chemical features responsible for their
visibility and commonly consonant with the writings of modern
color chemists. Due to the complexities of the color nomenclature
from the chemical structure system, the classification in terms of
application is often favorable. Chemical structures of dyes deter-
mine the colors, properties and uses; and provide the only
reasonable basis of a classification of dyes. There are different ways
for classification of dyes; it can be classified in terms of color,
chemical structure (functional groups) or application methods [53].
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
Some of these functional groups contain similar dyes with
distinctive structural features, but others, e.g., hydroxy-ketones or
natural coloring matters, are chemically heterogeneous. A more
sensible classification of dyes and related compounds requires
stricter adherence to chemical structure, placing chemically similar
compounds near to one another. The common dyes applied in the
textile industry are acid dyes, basic dyes, direct dyes, azo dyes,
naptha dyes, reactive dyes, mordant dyes, vat dyes, disperse dyes
and sulfur dyes [54], where azo derivatives based dyes are the
major class of dyes that are used in the industry today. Other than
that, dyes are also usually classified based on their particle charge
upon dissolution in aqueous application medium such as cationic
dyes which are basic dyes while the anionic dyes include direct,
acid and reactive dyes, and non-ionic dyes (dispersed dyes) [55].
Many of the dyes used in various industries are toxic and
carcinogenic, and this poses a serious exposure to aquatic living
organisms. The toxicity and impact of dyes released to the envi-
ronment through wastewater, therefore it has been extensively
studied [56,57]. Furthermore, because of the increasingly strict
restrictions on the organic composition of industrial effluents or
pollutants, it is an essential task to eliminate dyes from wastewater
before they can be discharged into the environment. However,
many dyes are difficult to decolorize or decompose, owing to their
synthetic origin and highly complex structure. These dyes usually
have many structural varieties, for example, acidic, basic, azo, diazo,
disperse, anthraquinone-based, naphtha-based and metal complex
dyes. As a result, traditional wastewater treatment technologies are
markedly ineffective in handling synthetic dye-contained waste-
water, because of the chemical stability of these pollutants [58]. A
wide range of technologies has been developed to remove syn-
thetic dyes from wastewater so as to reduce their impact on the
environment. Therefore, the chemical precipitation, adsorption on
organic or inorganic matrices, and decolorization by photocatalysis
and/or by chemical oxidation processes are some of the technolo-
gies currently being used for the removal of synthetic dyes [59].
2.3. Photocatalytic degradation of dyes for environmental
treatment
In few decades ago, the removal of dyes was practiced by
application of adsorbents based on the electronehole pair in-
teractions [60], the change in size and morphology of the photo-
catalytic materials has a positive effect on their properties like
surface area, photons carrying ability, followed by movement of
electrons and holes along the morphology [61,62]. Till today, many
researchers have demonstrated numerous photocatalytic activities
of various photocatalytic materials for degradation of different
organic compounds present in water including dyes [63e66]. From
all these studies based on the photocatalytic application for
degradation pollutant, it is evident that, the band gap, crystallinity,
morphology, phase composition, electronehole recombination
rate, penetration of light through photocatalytic materials, surface
area and adsorption capability of the dye on the surface of photo-
catalysts are the important parameters which help in the
enhancement of the photocatalytic activity [67,68]. Based on this,
researchers were fascinated toward the synthesis of higher surface
area photocatalysts which can provide higher surface and higher
adsorption of the dye on the surface of these materials.
Today, dyes form the foremost group of pollutants found in
wastewaters discharged from different chemical industries. It is
well-known that even 1 ppm concentration of dye can cause the
serious problems in water environments. In environment clean-up
applications, particularly using photocatalytic processes, various
types of semiconductor nanomaterials having different morphol-
ogies play a major role for the degradation or decolorization.
85
Decolorization of dye effluents has therefore received increasing
attention for the confiscation of dye pollutants, traditional physical
techniques (adsorption on activated carbon, ultrafiltration, reverse
osmosis, coagulation by chemical agents, ion exchange on syn-
thetic adsorbent resins, etc.) can generally be used efficiently
[69e72]. Nevertheless, they are non-destructive, since, they just
transfer organic compounds from water to another phase, thus
causing secondary pollution. Consequently, regeneration of the
adsorbent materials and post-treatment of solid-wastes, which are
expensive operations, are needed [73]. Due to the large degree of
aromatics present in dye molecules and the stability of modern
dyes, conventional biological treatment methods are ineffective
for decolorization, mineralization and degradation [74e77]. Pho-
todegradation [78,79] and photomineralization [80e82] involves
dye decomposition to some stable products and complete
decomposition by conformation of total organic carbon (TOC)
analysis to mineralization products such as CO2, H2O, N2, NO3
,
and NO2
etc.
3. General mechanism of photocatalytic degradation
3.1. Heterogeneous mechanism
Photocatalytic reactions proceeds through may be homoge-
neously or heterogeneously, but in recent years, the heterogeneous
photocatalysis is far more intensively studied because of its po-
tential use in a variety of environmental and energy-related ap-
plications as well as in synthesis of organic compounds. In
heterogeneous photocatalysis, the photocatalytic reaction implies
the previous formation of an interface between a solid photo-
catalyst (metal or semiconductor) and other medium (fluid or gas)
containing the reactants and products of the reaction. Therefore,
the term “heterogeneous photocatalysis” is mainly used in cases
where a light-absorbing photocatalyst is utilized, which is in con-
tact with either a liquid or a gas phase. It has attracted constant
research since its infancy considering the high number of excellent
articles, reviews and books devoted by many researchers on various
reactions of heterogeneous photocatalysis [83e85]. Heterogeneous
photocatalysis has proved to be an efficient tool for degrading both
atmospheric and aquatic organic contaminants such as dyes, pes-
ticides, and toxic organic molecules [86]. It uses the sunlight in the
presence of a semiconductor photocatalyst to accelerate the
remediation of environmental contaminants and destruction of
highly toxic molecules [87,88]. Here, we will restrict our attention
to the description of semiconductor-MSSNs mediated heteroge-
neous photocatalytic degradation of organic dyes and reports the
important accomplishments.
3.2. Homogeneous mechanism
Photocatalytic degradation reactions are carried out both under
homogeneous and heterogeneous conditions, but solid semi-
conductors is more extensively used because they are cheaper,
more robust, easily recovered and reused than soluble photo-
catalysts. Despite the advantages of heterogeneous photocatalysis,
homogeneous systems should not be underestimated and it is
possible that in the future these may play a greater role [89].
Photocatalysis may occur also in the homogeneous phase by using
molecules as the catalysts, since, molecular excited states are both
stronger reductants (through the donation of the electron pro-
moted in a vacant orbital) and stronger oxidants (by accepting an
electron in the empty site in the HOMO) with respect to the ground
state, leading again to an electron transfer process. Alternatively,
the structure of excited states may favor atom transfer. In the ho-
mogeneous photocatalysis, dyes show intensive bands not only in
86 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

the UV range but also in the visible range. However, their use is not Table 1
free from limitations, such as their difficult recovery after the re- The band gap values, corresponding wavelengths and structures of the different
semiconductor metal sulfide nanoparticles as photocatalysts.
action, their photostability and their possible toxicity. Probably for
these reasons, homogeneous photocatalysis is now in the pre- MSNSs Wavelength, nm Band gap, eV Absorption light Structure
liminary stage of application, although explorative and mechanistic ZnS 250e380 3.2e4.3 UV Cubic, Wurtzite
studies have been carried out. The proposed mechanism of pho- CdS 350e550 2.2e2.7 Visible Cubic, Hexagonal
tocatalytic degradation of organic dyes using semiconductor CuS 450e800 1.4e2.2 Visible-NIR Hexagonal
Ag2S 415e500 1.1e2.3 Visible-NIR Monoclinic
MSNSs under various light irradiations is shown in Fig. 1.
Bi2S3 400e900 1.1e1.46 Visible Orthorhombic
CoS 450e750 1.1e2.6 Visible Hexagonal
4. Basic principles of photocatalytic degradation of organic FeS 750e950 0.95e2.43 Visible Cubic
dyes using metal sulfide nanostructures PbS 400e550 1.2e1.6 Visible Hexagonal

Photocatalysis includes the basic photochemical reactions of

organic dyes, organic compounds, pesticides photodegradation,
disinfection of water and air, production of renewable fuels,
hydrogen generation, and organic compounds synthesis. In semi-
conductor nanostructures, the MSNSs are usually used as efficient
photocatalysts due to their capability in absorbing broad region of
visible and/or UV light, the combination of electronic structure,
charge transport characteristics and excited-state life-times. An
ideal photocatalyst should be highly photoactive, inexpensive,
photostable and non-toxic. Photocatalytic degradation of organic
pollutants by MSNSs, which have a harmful effect on the well-being
of mankind, has easily become the center point of research efforts
in today's scientific world. The dyes that are emitted from various
industries pose a severe environmental problem as the degradation
of these dyes is often very slow and conventional treatments are
mostly ineffective and not environmentally compatible. In this re-
gard, application of photocatalysis, especially photocatalysis using
semiconductor MSNS system, appears to be the most interesting
means than the more conventional chemical oxidation methods for
decomposition of toxic compounds to non-hazardous products
[90e94].
The basic photocatalytic (photophysical and photochemical)
principles underlying photocatalysis are already established and
have been reported in many literature [95,96]. The photocatalytic
reaction is initiated when the photoexcited electrons promoted
from the filled valence band of semiconductor photocatalyst to the
empty conduction band, as the absorbed photon energy, hʋ, equals
or exceeds the band gap of the semiconductor photocatalyst leav-
ing behind a hole in the valence band. Thus, together electron and
hole pair (e
ehþ) is generated. The process of semiconductor
photocatalysis basically involves the following stages such as light
energy of a certain wavelength is made to fall onto a semiconductor,
if the energy of the incident light is equivalent to the band gap
energy of the semiconductor, electrons would be excited from the
valence band to the conduction band of the semiconductor and
holes would be left in the valence band. These electrons and holes
could undergo subsequent oxidation and reduction reactions with
any species or other reactants, which might be adsorbed on the
surface of the semiconductor to give the necessary degradation
products.
Metal sulfide semiconductor nanostructures fulfill the re-
quirements of good photocatalysts in the heterogeneous photo-
catalytic degradation of dyes, and their electronic structures could
be explained by the band model, which is characterized by a filled
valence band (VB) separated from a vacant conduction band (CB) by
a forbidden energy gap, called band gap (Eg). The band gap energies
of semiconductors lie within the range of 1e4 eV; hence, these
semiconductor-based MSSNs materials meet the requirements of a
photocatalyst compared to metals and insulators. The unique
properties of semiconductor materials make them particularly
interesting for photocatalytic reactions for environmental applica-
tions. The band gap values, corresponding wavelengths, and
structures of the different semiconductor metal sulfide nano-
structured photocatalysts were shown in Table 1.
5. Modified metal sulfide photocatalysts for
photodegradation of organic dyes
5.1. Doped and heterojunction based nanosized ZnS photocatalysts
ZnS is an IIeVI compound semiconductor with direct and wide
band gap (3.6 eV) [97], which make it suitable as a transparent
photocatalytic material in the visible region. There are two

Fig. 1. The schematic representation of photocatalytic degradation mechanism of dyes using semiconductor metal sulfide nanostructures under light irradiation.
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
structures of ZnS, a-phase (hexagonal wurtzite structure) and b-
phase (cubic sphalerite structure) [98]. It has traditionally shown
extraordinary versatility, novel fundamental properties and diverse
applications such as field emitters, field effect transistors (FETs), p-
type conductors, photocatalysts, chemical and biosensors
(including gas sensors), nonlinear optic devices and nano-
generators [99]. ZnS nanostructured materials have been prepared
using various physicochemical methods such as hydrothermal
method, solvothermal method, microwave method and coprecipi-
tation methods with a view of their potential applications. ZnS has
a hexagonal structure and forms nanosheets or nanorods with large
specific surface area [100,101]. An application of non-toxic ZnS
semiconductor as a photocatalyst is an efficient tragedy for the
elimination of environmental pollutants especially for degradation
of organic dyes from water. ZnS rapidly generates electronehole
pairs under photoexcitation and exhibits a high physical stability
under UV light. Due to its non-toxicity, ZnS is now used in waste-
water treatment as a photocatalyst in the degradation of organic
contaminants such as dyes, halogenated derivatives, and p-nitro-
phenol [102,103].
Although, semiconductor-based metal sulfides are known for
their good photocatalytic behavior, among them ZnS is not
competent photocatalyst, because of its high energy band gap
(3.66 eV), which corresponds to less than 340 nm i.e., it is active
only in 4% of the incoming solar light [104]. Attempts were made by
different research groups for enhancing the photocatalytic activity
of ZnS with different morphologies e.g., cubic [105], nanorods
[106], nanotubes [107], nanobelts [108] and nanowires [109]. The
results were not considerably productive; a very small shift in
wavelength towards visible region was observed with change in
morphologies. Yang et al. investigated the preparation of ZnS, ZnS/
CuS and ZnS/CuS-rGO nanocomposites are shown in Fig. 2 [425]. In
addition, the as-prepared ZnS nanocomposites were characterized
carefully and used as photocatalysts to degrade EB, MB, RhB, MO
Fig. 2. The schematic illustration of the synthesis of ZnS, ZnS/CuS and ZnS/CuSerGO (Ref. [425]).
87
and MG under simulated sunlight irradiation. Porta et al. [110] re-
ported the preparation of single crystalline hexagonal wurtzite
phase of ZnS NPs using different precursors, which greatly trans-
formed the absorbance edge from UV to visible region for photo-
degradation of RhB having absorbance maxima at 554 nm. In the
photocatalytic reaction, 80 ml of 10 mg L
1 of RhB at pH 6.0 was
mixed with 60 mg of the catalyst and irradiated with a UV light
placed in a photochemical reactor, which was set at a distance of
20 cm from the beaker containing the suspension, was exposed to
210 min and 97% dye was successfully degraded which was
monitored by a sharp decrease in the absorption maxima at
554 nm. Hanifehpour et al. [211] described the synthesized
praseodymium-doped ZnS NPs with a good uniform size of the
particles through TEM images are shown in Fig. 3, it shows spher-
ical shape with polycrystalline nature. The morphology and size can
be controlled by using different capping agents, which significantly
transforms the absorption from UV to visible region [111,112].
Heterojunctions and dopants based ZnS NPs play a vital role in
enhancing the photocatalytic activity of ZnS NPs in the degradation
of dyes. Pouretedal et al. investigated that the absorption studies of
the ZnS, ZnS:Mn (2%), ZnS:Ni (6%) and ZnS:Cu (10%) exhibited a
blue shift in comparison to the ZnS microstructure having a
shoulder at 350 nme310 nm for nanostructures. From this study, it
can be attributed to the formation of quantum size doped and
undoped ZnS nanostructures and under the application of energy
source electron/hole pairs were generated and the life-time of
these free carriers largely depends upon the dopant. The results
show that maximum photodegradation can be achieved with
ZnS:Mn (2%), ZnS:Ni (6%) and ZnS:Cu (10%), because different
dopants have different capacity to change the life-time of the
charge carriers, because it depends on the position of dopant inside
the lattice [113]. Recently, Reddy et al. [114] reported that the CdS/
ZnS coreeshell heterojunction structures were prepared, which is
exhibited as an excellent photocatalyst for the degradation of MO
88 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

Fig. 3. (aed) TEM images of praseodymium-doped ZnS NPs (Ref. [211]).

Fig. 4. The photocatalytic degradation of methylene blue (MB) (a); degradation efficiency (b); plot of ln (C0/C) as a function of UV irradiation time for the photocatalysis of MB
solution containing ZnS and ZnSeRGO composites with different weight addition ratios of RGO (c); reusability of the ZnSe43.6 wt% RGO composite in the UV light degradation of
the MB solution (d) (Ref. [225]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 89

(concentration: 5 ppm) using the prepared catalyst of 5 mg L
1. The
result exhibited that the CdS/ZnS core/shell nanoparticles had the
highest photocatalysis activity, in which more than 90% of the MO
was degraded within 90 min compared to CdS (74.5%) and ZnS
(55.4%) respectively. Feng et al. [225] also described the photo-
catalytic degradation of MB under the irradiation of UV light with
heterojunction based ZnS and ZnS-RGO composites and the
degradation efficiency of prepared composites on the photo-
degradation of MB as a function of time, plot of ln (C0/C) and
reusability of the ZnS-43.6 wt% RGO composite was shown in Fig. 4.
The prepared doped and heterojunction based nano-sized ZnS NSs
based photocatalysts involved upto till date in the photocatalytic
degradation of various dyes under different light sources are
summarized in Table 2.
5.2. Doped and heterojunction based nanosized CdS photocatalysts
CdS is considered as a classic IIeVI semiconductor and it has a
direct band gap of 2.43 eV at room temperature is known to be the
best semiconductor and has given considerable attention by the
researchers for potential applications [115]. Nowadays nano-
structured CdS is a current issue due to the large variety of appli-
cations, for instance, in solar cells, as a photocatalyst, as a biotracer
tumor marker, as chemical sensor [116e118], etc. Recently, Lu et al.

Table 2
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based ZnS NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

ZnS NPs Hg-lamp 4.29 RhB 555 10
4 M 65 [187]

ZnS/rGO W-lamp 3.4 RhB 554 10 mg/L 97 [188]
ZnS/Se UV 3.3 MO 460 40 mM 95 [189]
ZnS NPs UV 3.2 RB5 598 20 ppm 100 [190]
ZnS/PANI UV 3.14 Rh6G 524 4 mg/L 80.62 [191]
ZnS/Cu UV 3.6 MB 665 5 ppm 56 [192]
ZnS/GO UV 3.9 BB 465 10 ppm 90.61 [193]
ZnS QDs solar 3.07 BG 625 10 ppm 88 [194]
ZnS NPs Visible 3.6 MO 462 5 ppm 55.4 [114]
ZnS/CdS Visible 2.15 MO 462 5 ppm 90 [114]
ZnS/ZnFe2O4 Xe-lamp 2.2 MO 463 0.001 M 82 [195]
ZnS NPs UV 3.45 RhB 554 10 mg/L 97 [110]
ZnS/Cr Visible 2.97 MO 465 1  10
4 M 74.28 [196]
ZnS/SnO2 Xe-lamp 3.7 RhB 554 10 mM 99 [197]
ZnS NSs UV 3.62 MB 664 6 mg/L 88.49 [198]
ZnS NPs Hg-lamp 4.03 VBR 591 10 mg/L 96 [199]
ZnS/SnS Hg-lamp 4.2 CR 496 12 ppm 61 [200]
ZnS/SnS/FA Hg-lamp 4.05 CR 496 12 ppm 99 [200]
ZnS/CQDs Visible 3.01 ARS 424 10 mg/L 89 [201]
ZnS/ChPA solar 4.12 CR 495 2  10
5 M 75 [202]
ZnS/ChPA solar 4.12 MO 464 2  10
5 M 69 [202]
ZnS/rgo W-lamp 3.64 MB 664 1  10
4 M 55.23 [203]
ZnS/rgo W-lamp 3.64 RhB 554 1  10
4 M 90.37 [203]
ZnS/TNR Hg-lamp 3.57 ST 520 10 ppm 97 [204]
ZnS/Cd Solar 2.44 ARS 502 5  10
5 M 96.7 [205]
ZnS NPs UV 3.80 MB 666 10 mg/L 86 [206]
ZnS NPs Hg-lamp 3.44 MO 464 10 mg/L 96.8 [207]
ZnS NPs Visible 3.96 CR 487 1.5 mmol 54 [208]
ZnS NPs Visible 3.96 MG 617 1.5 mmol 65 [208]
ZnS NPs UV 3.64 MO 462 10 mg/L 97.4 [209]
ZnS NPs UV 3.64 RhB 553 10 mg/L 70.4 [209]
ZnS NPs Visible 3.75 CR 497 30 mg/L 98.78 [210]
ZnS/Pr Visible 3.72 RB19 592 10 mg/L 86.64 [211]
ZnS NSs UV 3.38 MB 664 12 mg/L 92 [212]
ZnS/SnO2 Solar 3.24 RhB 554 10 mg/L 95 [213]
ZnS/CNTs Visible 3.6 MO 464 20 mg/L 96.04 [214]
ZnS/GR Hg-lamp 3.41 MO 462 10 mg/L 93 [215]
ZnS NSs Solar 3.9 RhB 554 5 mM 83 [216]
ZnS/Fe NPs Hg-lamp 3.78 RhB 545 1  10
5 M 93.06 [217]
ZnS/PEG Solar 3.8 XO 570 5  10
5M 87.24 [218]
ZnS NPs Solar 3.54 RhB 553 20 mg/L 70 [219]
ZnS NPs UV 3.54 CV 438 1  10
6 M 30 [219]
ZnS/Ni Visible 3.74 MB 663 150 ppm 94 [220]
ZnS NRs UV-lamp 3.51 XB 588 25 mg/L 88.4 [221]
ZnS NPs Xe-lamp 3.61 SO 520 10 mg/L 94 [222]
ZnS/TGA Hg-lamp 3.24 MO 462 20 mg/L 95.2 [223]
ZnS/CuS Visible 1.98 MB 664 2  10
5 M 100 [224]
Zns/rGO Hg-lamp 3.56 MB 664 1  10
5 M 98.98 [225]
ZnS NCs UV 4.92 MO 463 5  10
5 M 80 [226]
ZnS/ZnO Visible 4.67 MB 662 0.002 g/L 74 [227]
ZnS NSs Hg-lamp 3.8 EB 517 5  10
5 M 70 [228]
ZnS/CuS Xe-lamp 3.42 RhB 550 20 mg/L 98 [229]
ZnS/GQD Xe-lamp 3.40 RhB 554 10 mM 72 [230]
ZnS/CuS Xe-lamp 3.14 EB 517 50 mg/L 99.24 [425]
ZnS/CuS Xe-lamp 3.14 MB 664 50 mg/L 99.19 [425]
ZnS/CuS Xe-lamp 3.14 RhB 554 50 mg/L 94.65 [425]
ZnS/CuS Xe-lamp 3.14 MO 464 50 mg/L 83.44 [425]
ZnS/CuS Xe-lamp 3.14 MG 617 50 mg/L 78.51 [425]
90 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

[426] demonstrated that the formation of MWCNTs enfolded CdS
NPs under ultrasonication and its schematic design was shown in
Fig. 5. CdS have widespread applications in the construction of
photo-electronic devices, in the field of medicine as bio-imaging and
biosensors because of its low toxicity and optoelectronic properties
and also is the best visible light active semiconductor-based pho-
tocatalyst. Many physical and chemical techniques are used to
synthesize CdS nanoparticles as films, powders, colloids, nanofibers,
nanorods, among others. Because of the unique property of size-
dependent physical and chemical nature, it is of the great interests
of the researchers. Li et al. [427] reported the synthesized CdS NPs at
different temperatures (230e285  C) with uniform size and high
crystallinity of the particles through HRTEM are shown in Fig. 6. The
CdS NSs exhibits tremendous photocatalytic activity in UV and
visible regions due to their high surface area, absorption in a visible
range, small size particles and other optical studies.
In general, the CdS nanostructures can be used as an excellent
material for dye degradation because its band gap and absorption
in visible region. However, the low separation efficiency of the
charge carriers i.e., electrons/holes pairs and the corrosion prob-
lems associated with it, are the some of the drawbacks for using
CdS in environmental remediation. Indefatigable attempts were
made for enhancing the photocatalytic activity of the CdS by dop-
ants and other than CdS semiconductor nanostructures. Chen et al.

Fig. 5. The schematic strategy of the formation of CdS/MWCNTs (Ref. [426]).

Fig. 6. TEM images of CdS NPs synthesized at various temperatures: (a) 230  C, (b) 250  C, (c) 270  C, and (d) 285  C; the inset in (d) shows the related HRTEM image,
demonstrating high crystallinity (Ref. [427]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
reported the fast degradation of RhB under visible light irradiation
by using the coreeshell nanospheres of CdS/carbon under visible
light irradiation [119]. Therefore, the nanostructured CdS is a suit-
able material to be used as the photocatalyst to study the degra-
dation of dyes. The enhanced photocatalytic activity of the CdS
nanospheres against MB has been successfully reported [120] and it
showed the 96% degradation of MB for 180 min under visible light
and there was observed a shift in the peak. Similarly, CdS hollow
spheres having average diameter of 10 nm, were used by Lou et al.
[121] for the degradation of RhB (concentration: 50 mL of
1  10
5 mol L
1) providing intense broad peak at 533 nm, with the
increase in exposure time successive reduction in peak was
observed, corresponding to the degradation of dye, which
completely disappears after 45 min. Eventually, the Ni-doped CdS
had better activity than the undoped CdS, and highest activity was
observed with 1.2 mole% Ni-doped CdS and degradation time was
reduced from 45 min to just 35 min after irradiation. The enhanced
activity can be conveniently related to the formation of special
structure, and effective separation of the already formed photo-
generated carriers after doping with Ni [122].
Many heterojunction based CdS photocatalysts have been
developed, including CdS/WO3, MoS2/CdS, CdS/g-C3N4, CdS/BiVO4,
and CdS/Ni which were prepared via different methods and
exhibited enhanced photocatalytic performance than the CdS NSs
[123e126]. However, for the high enhancement of photocatalytic
degradation against MB and MV under 300 W Xe-lamp with a
420 nm cutoff filter. 0.1 g photocatalysts were added into 100 mL
dyes solution (concentration: 10 mg L
1) in a Pyrex photocatalytic
reactor by CdS/MnWO4 heterojunction photocatalyst [127]. There-
fore, the exploration of photocatalytic mechanism and potential
application of this heterojunction based CdS NSs are highly needed.
The experimental results showed that the CdS/MnWO4 hetero-
junctions exhibited superior photocatalytic activities in decom-
posing MB and MV under visible light irradiation. The CdS/MnWO4
has an excellent photocatalytic activity on the degradation of MV
than that over pure MnWO4, while 91% MB, 97% MV can be
degraded by the CdS/MnWO4 (0.5 mmol of CdS) over the same time
duration. These results could be ascribed to the synergetic effects of
light absorption and heterojunction structure of CdS/MnWO4.
Recently, Fan et al. [243] established the efficient photocatalytic
degradation of RhB for npg-C3N4, pure CdS QDs and CdS QDs/npg-
C3N4 composites and cycling runs for the photocatalytic degrada-
tion of RhB in the presence of the sample of CdS/CN-10% are shown
in Fig. 7. The CdS, doped-CdS and heterojunction based CdS NSs as
Fig. 7. (a) The photocatalytic degradation of RhB for npg-C3N4, pure CdS QDs and CdS QDs/npg-C3N4 composites and (b) cycling runs for the photocatalytic degradation of RhB in the
presence of the sample of CdS/CN-10% (Ref. [243]).
91
heterogeneous photocatalysts involved in the photocatalytic
enhancement of the dyes degradation under light are listed in
Table 3.
5.3. Doped and heterojunction based nanosized CuS photocatalysts
In particular, CuS are of great interest due to their extraordinary
optical properties which can bring many potential applications. The
stoichiometry of CuS varies from CuS2 at the copper-deficient side
to Cu2S at the copper-rich side. The primary phases of copper sul-
fide minerals are Cu2S and CuS. Eight copper sulfide minerals have
been identified to date such as covellite (CuS), yarrowite (Cu1.12S),
spionkopite (Cu1.40S), geerite (Cu1.60S), anilite (Cu1.75S), digenite
(Cu1.80S), djurleite (Cu1.97S), and chalcocite (Cu2S). Among them,
CuS exists in different morphologies possessing different band gap
values e.g., CuS microspheres, nanotubes, nanoflakes and nano-
particles with the average band gap of 2.08, 2.06, 2.16 and 1.88 eV,
respectively. The covellite CuS is one of the most intensively studied
copper sulfides due to its unique physical and chemical properties
and its potential applications in many fields such as photocatalysis
[128], low-temperature superconductors [129], optical filters and
superionic materials [130], nano-switches [131], lithium-ion bat-
teries [132], sensors [133], and thermoelectric cooling material
[134]. Wang et al. [289] revealed that the general schematic illus-
tration for the construction pathway for CCNeCuS nanoflowers and
shown in Fig. 8. The studies on photocatalysis of covellite CuS focus
mainly on visible light source due to its narrow band gap and good
optical absorption properties in the visible-NIR region. The photo-
catalytic activity of CuS semiconductor NSs depends on the size,
surface area and morphology. Therefore, the size and shape of the
synthesized CuS NPs in organic solution at different temperatures
(220e260  C) by TEM images is shown in Fig. 9 [428]. In particular,
hierarchical CuS NSs have demonstrated promising application in
photocatalysis of degradation for organic dyes [135].
CuS has strong affinity for absorption of visible light and
examine the photocatalytic degradation of various dyes consid-
ering under various pH conditions; cationic dyes like MB, MG, RhB,
anionic dyes like methyl orange (MO), eosin E and neutral dye like
methyl red (MR) (concentration: 30 mL, 10
5 M) with the prepared
CuS hexagonal stacked plates having edge length of 200 nm and
thickness of 23.44 nm by Basu et al. [136]. Fu et al. reported the
visible-light photocatalytic activities of CuS NSs and commercial
P25 TiO2 were evaluated through the removal of MB with an initial
dye concentration of 2  10
5 M [137]. A photocatalytic reactor
92 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

Table 3
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based CdS NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

CdS/Fe2O3 Xe-lamp 2.4 MB 664 5 mM 94 [231]

CdS/Ni Solar 2.34 MB 663 1 mg/L 70 [232]
CdS/TiO2 Xe-lamp 2.4 MO 464 10 ppm 100 [233]
CdS/TiO2 Xe-lamp 2.4 RhB 554 10 ppm 100 [233]
CdS/C60 Visible 2.61 RhB 553 10 mg/L 97 [234]
CdS/Bi Visible 2.51 MO 464 10 mg/L 93.7 [235]
CdS/DETAMWCNTs LED-lamp 2.33 MB 663 20 mg/L 89 [236]
CdS/Ni UV 2.38 MO 464 15 ppm 98 [237]
CdS NPs Xe-lamp 2.3 RhB 552 10 mg/L 92.5 [238]
CdS NSs Solar 2.67 CR 497 50 mg/L 99.3 [239]
CdS/MoS2/TiO2 Xe-lamp 2.7 MB 664 5 mg/L 72 [240]
CdS/TiO2 Xe-lamp 2.9 MB 664 5 mg/L 59 [240]
CdS/GR Visible 2.25 MB 664 10 mg/L 94.5 [241]
CdS/GR Visible 2.25 MO 462 10 mg/L 80 [241]
CdS/GR Visible 2.25 RhB 553 10 mg/L 91 [241]
CdS/TiO2 Xe-lamp 3.2 RhB 554 10 mg/L 96.8 [242]
CdS/npg-C3N4 Xe-lamp 2.61 RhB 554 10 mg/L 88.2 [243]
CdS NPs UV 2.25 RhB 553 20 mg/L 83 [244]
CdS/RGO Xe-lamp 2.51 RhB 554 12 ppm 93 [245]
CdS/TiO2 Hg-lamp 2.28 MB 664 12 mg/L 92 [246]
CdS NPs Visible 2.45 MB 663 10 mg/L 83.8 [247]
CdS QDs Solar 2.62 AZ 334 250 ppm 76 [248]
CdS/BiVO4 NCs Hg-lamp 2.71 MG 617 15 mg/L 98.3 [249]
CdS/C3N4 Visible 2.37 MO 464 5 mg/L 99 [250]
CdS NRs UV 2.64 MO 464 10 mg/L 93 [251]
CdS/Ag W-lamp 2.41 MB 662 10 ppm 95.35 [252]
CdS NPs Xe-lamp 2.68 RhB 554 2.6  10
5 M 99 [253]
CdS/TiO2 Xe-lamp 2.7 MO 462 10 mg/L 70 [254]
CdS/TiO2 Xe-lamp 2.64 RhB 553 5 mg/L 99.9 [255]
CdS/ZnS Visible 3.15 AB 602 1 g/L 86.5 [256]
CdS/BN Xe-lamp 2.71 RhB 553 100 mg/L 96 [257]
CdS/AgS/TiO2 UV 2.51 MB 663 20 mg/L 70 [258]
CdS NCs Xe-lamp 2.34 MO 465 10 mg/L 70 [259]
CdS NCs Xe-lamp 2.34 MB 664 50 mg/L 90 [259]
CdS NCs Xe-lamp 2.34 RhB 554 20 mg/L 93 [259]
CdS/TiO2 Solar 1.99 BG 624 1 mg/L 97 [260]
CdS/TiO2 Solar 1.99 MB 664 1 mg/L 94 [260]
CdS/Ce3þ Xe-lamp 2.2 MB 663 12 mg/L 93.2 [261]
CdS/Zn2þ Xe-lamp 2.24 MB 663 12 mg/L 91.2 [261]
CdS/Cu2þ Xe-lamp 2.26 MB 663 12 mg/L 95.5 [261]
CdS/TiO2/SiO2 Visible 3.13 MB 664 10 mg/L 85 [262]
CdS NPs Visible 2.66 RR 501 25 mg/L 96.64 [263]
CdS NSs Xe-lamp 2.225 RhB 554 10 mg/L 98 [264]
CdS NSs Xe-lamp 2.225 MB 665 10 mg/L 93.3 [264]
CdS NSs Xe-lamp 2.225 MO 465 10 mg/L 92 [264]
CdS NPs UV 3.15 MO 462 10 mg/L 98 [265]
CdS NFs Visible 2.53 MB 663 1  10
5 M 82 [266]
CdS NPs Xe-lamp 2.24 MB 664.5 5  10
6 M 60 [267]
CdS/WO3 Visible 2.31 MO 467 10 mg/L 82 [268]
CdS/TiO2/WO3 Visible 2.30 MO 467 10 mg/L 94 [268]
CdS/ZnO W-lamp 3.2 MO 464 5 mg/L 94.6 [269]
CdS NPs Solar 2.17 MR 394 2  10
5 M 82.59 [270]
CdS NPs Solar 2.62 MO 462 5  10
6 M 75.33 [271]
CdS/TiO2 W-lamp 2.54 MB 664 1.5  10
2 g/L 42 [272]
CdS NSs Xe-lamp 2.4 MB 660 44 ppm 87 [273]
CdS NSs Xe-lamp 2.4 RB 553 1  10
5 M 100 [121]
CdS/SnO2 W-lamp 2.98 MO 465 50 ppm 95.2 [274]
CdS/Ni Hg-lamp 2.66 MB 663 10 ppm 100 [122]
CdS/Bi Xe-lamp 2.23 MB 664 10 mg/L 95 [275]
CdS NPs Solar 2.43 MB 668 5 ppm 79.92 [276]
CdS/Cu Solar 1.82 MB 668 5 ppm 90.09 [276]
CdS NPs Visible 2.61 EY 516 2  10
5 M 91.12 [277]
CdS NPs Visible 2.61 MB 664 2  10
5 M 85.53 [277]

equipped with a xenon lamp and a 430 nm cut-off filter were used.
Significantly, the reaction was largely activated by using CuS NSs.
An approximate 53% of the dyes are removed from the solution
after 2 h illumination. The photocatalytic activity of Cu2S was
evaluated against Active Brilliant Red X-3B, for nanoparticles,
nanowires and nanoflowers to 11.7%, 20.3% and 50.1%, respectively
[138]. Recently, Shamraiz et al. [139] reported the degradation of
MG, MB, MO, MV and RhB with CuSeCu2S hybrid nanoparticles.
The photocatalytic activity of the CuS/ZnO/CFs heterostructures
was also investigated under the irradiation of visible and simulated
solar light, and they displayed high performance and stability for
the photodecomposition of MB (concentration: 50 mL of 10 mg L
1)
and it was 98% degraded in 120 min of irradiation [140].
Copper chalcogenide composites such as CuS NCs have attracted
significant attention because of their unique physicochemical
properties and extensive potential applications in various fields. Hu
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 93

Fig. 8. The schematic illustration of the possible construction pathway for CCNeCuS NFs (Ref. [289]).

Fig. 9. (aed) TEM images of copper sulfide synthesized in organic solution at a) 220, b) 230, c) 240 and d) 260  C (Ref. [428]).

et al. [141] reported that the CuS/RGO composites were innova-
tively synthesized by a facile one-step solvothermal approach. The
photodegradation of MB (concentration: 50 mL, 15 mg L
1) was
carried out to evaluate the photocatalytic activity of the as-
obtained photocatalysts (0.1 g) under Xe-lamp irradiation in
180 min. The composites exhibited enhanced photocatalytic
performance and stability for MB even without the assistance of
H2O2 due to the integrative effect of CuS and RGO. Moreover, CuS/
RGO catalysts of different weight dispersed in MB solution were
also tested for the degradation of MB. Chen et al. [284] confirmed
the degradation rate of RhB under visible-light irradiation
(>420 nm) without catalyst and in the presence of g-C3N4, CuS and
94 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

g-C3N4/CuS NCs and determination of rate constants (k) of the
photodegradation of MB in the presence of as-prepared samples,
error bars were based on the standard deviations of three parallel
experiments are shown in Fig. 10. Zhao et al. [142] synthesized Cu2S
microspheres and microrings and investigated their photocatalytic
ability in MB degradation. The authors reported that 70% and 76% of
MB was degraded using Cu2S microspheres and Cu2S microrings,
respectively, after a long time (6 h). The photocatalytic activity of
various doped and heterojunction based CuS NSs as heterogeneous
photocatalysts for the degradation of various dyes under light ir-
radiations is summarized in Table 4.
5.4. Doped and heterojunction based nanosized Ag2S
photocatalysts
Ag2S is a direct, narrow-band gap semiconductor with good
chemical stability, excellent photoelectric and thermoelectric
properties, and has a band gap of Eg z 1.1 eV at room temperature
[143]. Ag2S has been recognized as having three phases in its nat-
ural solid bulk state such as monoclinic acanthite (a-phase) that is
stable below 179  C, body-centered cubic (bcc) so-called argentite
(b-phase) that is stable above 180  C, and a high-temperature face-
centered cubic structure (g-phase) that is stable above 586  C [144].
Tan et al. [429] reported the general synthetic procedure of mes-
oporous Ag2S nanospheres and as shown in Fig. 11. Ag2S NPs were
extensively used in the fields of photocatalysis such as the photo-
catalytic decomposition of dyes [145], photocatalytic H2 production
[146], solar cell [147] owing to its good chemical stability and
excellent optical limiting properties [148]. For photocatalytic ap-
plications, various Ag2S-based nanostructures, for example, the
Ag2S-encapsulated mesoporous MCM-41 NPs, porous Ag2S NP
membranes, poly(amidoamine)-functionalized carbon nanotube-
Ag2S QDs and the Ag2SeTiO2 donor-acceptor systems have been
designed and fabricated. It was finally shown, to enhance photo-
catalytic activities toward water splitting and degradation of
persistent organic pollutants (POPs) such as phenol, RhB, MO and

Fig. 10. (a) The degradation rate of RhB under visible-light irradiation (>420 nm) in the absence and presence of g-C3N4, CuS and g-C3N4/CuS NSs, (b) plot of ln(C/C0) vs irradiation
time of all samples (RhB), (c) the rate constants k of the photodegradation of RhB in the presence of as-prepared samples, (d) the degradation rate of MB under visible-light
irradiation (>420 nm) in the absence and presence of g-C3N4, CuS and g-C3N4/CuS NCs, (e) plot of ln(C/C0) vs irradiation time of all samples(MB) and (f) the rate constants k of
the photodegradation of RhB in the presence of as-prepared samples (Ref. [284]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 95

Table 4
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based CuS NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

CuS NPs Visible 1.77 MB 664 5.8 mg/L 85.4 [278]

CuS NPs Xe-lamp 2.32 RhB 554 10 mg/L 83.22 [279]
CuS/Ni NPs Xe-lamp 1.97 RhB 554 10 mg/L 98.46 [279]
CuS/Fe Xe-lamp 2.02 RhB 554 10 mg/L 98.53 [280]
CuS NPs Xe-lamp 2.05 RhB 554 10 mg/L 84.87 [280]
CuS/TiO2 W-lamp 2.12 AO-7 483 5 mg/L 44.9 [281]
CuS/CdS/TiO2 W-lamp 2.07 AO-7 483 5 mg/L 100 [281]
Cu2S US 2.20 MB 664 25 mg/L 100 [282]
CuS/TiO2 Solar 2.50 MG 621 5  10
6 M 78 [283]
CuS/g-C3N4 Xe-lamp 2.69 RhB 554 10 mg/L 99.6 [284]
CuS/g-C3N4 Xe-lamp 2.69 MB 665 10 mg/L 99 [284]
CuS NPs Xe-lamp 1.86 RhB 554 10 mg/L 40 [284]
CuS NPs Xe-lamp 1.86 MB 665 10 mg/L 28 [284]
CuS QDs Xe-lamp 1.87 RhB 553 10 mg/L 60 [285]
CuS NPs Xe-lamp 2.27 RhB 553 10 mg/L 100 [285]
CuS/C NP US 1.91 BPB 590 10 mg/L 96.14 [286]
CuS/C NP US 1.91 MB 664 10 mg/L 99.34 [286]
CuS/TiO2 UV 2.73 MB 662 20 mg/L 60 [287]
CuS UV 1.74 MB 662 20 mg/L 33 [287]
CuS W-lamp 1.45 MB 664 0.5 g/L 100 [288]
CuS NFs Visible 2.45 RhB 554 10 mg/L 92.6 [289]
CuS/ZnS Xe-lamp 1.86 MB 664 10 mg/L 98 [290]
CuS/ZnS Xe-lamp 1.86 RhB 554 20 mg/L 99 [290]
CuS/Bi2S3 Xe-lamp 1.72 RhB 560 10 mg/L 45 [291]
CuS/Cu NPs Xe-lamp 1.54 MB 664 0.02 M 90 [292]
CuS NPs Xe-lamp 1.91 MB 664 10 ppm 99 [293]
CuS NCs W-lamp 2.2 RhB 554 20 mg/L 93 [294]
CuS/TiO2 Visible 2.61 MB 663 10 mg/L 79.09 [295]
CuS/ZnS Xe-lamp 1.86 MB 662 10 ppm 95.51 [296]
CuS NPs Solar 2.02 MB 664 2  10
5 M 99.2 [297]
CuS/CdS Xe-lamp 2.14 MO 464 10 mg/L 93 [298]
CuS/rGO Visible 2.19 MB 663 20 mg/L 99.27 [299]
CuS NFs Solar 1.94 MB 604 400 mg/L 94.2 [300]
CuS NFs Solar 1.94 RhB 553 400 mg/L 95 [300]
CuS NPs Solar 1.7 MB 604 400 mg/L 96 [301]
CuS NPs Solar 1.7 RhB 553 400 mg/L 94 [301]
CuS NDs Xe-lamp 1.75 RhB 560 2.5 mg/L 93.23 [302]
Cu2S NCs Visible 1.8 CR 495 0.5  10
3 M 90 [303]
CuS/H2O2 X-lamp 1.71 MB 664 10 mg/L 94.2 [304]
CuS NSs Solar 1.97 MB 604 400 mg/L 96.5 [305]
CuS/ZnS Xe-lamp 3.66 MB 663 30 mg/L 97 [306]
CuS NPs Solar 1.54 MB 664 2  10
5 M 90.29 [307]
CuS NPs Solar 1.54 RhB 553 2  10
5 M 69.23 [307]
CuS NPs Solar 1.54 EY 516 2  10
5 M 91.97 [307]
CuS NPs UV 1.54 CR 498 2  10
5 M 75.47 [307]
CuS NPs Visible 1.54 MB 664 2  10
5 M 85.13 [307]
CuS NPs UV 1.54 EY 516 2  10
5 M 79.49 [307]
CuS NPs Solar 1.54 CR 498 2  10
5 M 60.35 [307]
CuS NPs Visible 1.54 RhB 553 2  10
5 M 60.37 [307]
CuS NTs UV 2.06 MB 663 2  10
5 M 97.4 [308]
CuS/TiO2NCs Xe-lamp 3.12 MB 664 10 mg/L 94 [309]
CuS NPs solar 2.11 MB 662 20 mg/L 90 [310]
CuS/CdS NCs W-lamp 2.27 MB 664 2  10
5 M 89.5 [311]
CuS NFs X-lamp 2.13 RB 553 5  10
6 M 90 [312]
CuS NPs Solar 2.25 SO 519 50 mg/L 80.53 [313]

Fig. 11. The schematic illustration of the synthetic procedure of mesoporous Ag2S nanospheres (Ref. [429]).
96 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

MB. Ag2S nanoparticles exhibit remarkable photocatalysis due to

their size, surface area, binding energy, optical studies and were
characterized by various techniques.
Ag2S NPs are unstable under ordinary conditions, because as the
particle size decreases the stability of the prepared clusters or
particles decreases. The surface energy increases with the decrease
in particle size, which compel the clusters or nanoparticles to
agglomerate. Luckily, using zeolites with well-defined micro-
cavities, it is possible to control the size of the synthesized Ag2S
NPs. Pourahmad et al. [149], successfully reported the photo-
catalytic activity of Ag2S, and Ag2S encapsulated in mesoporous
material MCM-41 against MB. When used separately for degrada- Fig. 13. The excitation and charge transfer processes among TiO2 particles, Ag2S par-
tion of MB, the degradation of MB was only 41% and 15% for Ag2S ticles, and graphene nanosheet (Ref. [324]).
and MCM-41, respectively. But, when Ag2S NPs were incorporated
in MCM-41 the activity readily increased to 94%. When 25 mL of
0.16e3.2 ppm concentration of MB, under various pH conditions the degradation of RhB with the presence of 4% GR/Ag2S material
from 3 to 12 were subjected to degradation by the synthesized and the results were shown more than 80% RhB degradation in 3 h
Ag2S/MCM-41 composite, having the average surface area of irradiation time (Fig. 14) [340]. The efficient photocatalytic degra-
700 m2 g
1. The degradation of MB for 60 min irradiation showed dation of various dyes exhibited using doped and heterojunction
the highest efficiency at pH 8 i.e., slightly alkaline medium. Aazam based nano-sized Ag2S photocatalysts are listed in Table 5.
[150] reported the TEM images of synthesized 1 to 4 wt.% of Ni-
doped Ag2S NPs (Fig. 12) and its photocatalytic performance of 5.5. Doped and heterojunction based nanosized Bi2S3
the Ag2S and Ni/Ag2S. These samples were examined in the photocatalysts
degradation of MB dye under visible light. The optimization of re-
action conditions led to the conclusion that 3 wt% Ni/Ag2S with the Recently, much attention has been paid to bismuth chalcogen-
use of 1.2 g of the catalyst in 1000 mL of a 140 mg MB dye solution ides, due to their high photocatalytic activities in the degradation of
yielded 100% degradation of the MB dye within 40 min under dyes. Among these bismuth chalcogenides, Bi2S3 has received
visible light irradiation. Meng et al. [324] demonstrated the exci- considerable attention in photocatalysis because of its unique op-
tation and charge transfer processes among TiO2 particles, Ag2S tical properties [151,152] and band gap (1.3 eV). Recently, many
particles, and graphene nanosheet and as shown in Fig. 13. Based on researchers have paid much attention to the photocatalytic activity
this graphene modified Ag2S NCs, these used as photocatalysts for of Bi2S3-based NSs. For example, Chen et al. [153] investigated that

Fig. 12. (aed) TEM images of Ni/Ag2S NPs, where wt% of Ni is 1 (A), 2 (B), 3 (C) and 4 (D) (Ref. [150]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
Fig. 14. (a) Photocatalytic activities of GR/Ag2S composites, (b) their kinetic constants, (c) COD data of RhB with the presence of 4% GR/Ag2S photocatalyst and (d) its cycling runs
(Ref. [340]).
a simple wet chemical method was employed to synthesize Bi2S3
hierarchical nanostructure using thioglycolic acid as a capping
agent. The obtained samples were used as photocatalysts for the
degradation of MO. The results indicated that the prepared Bi2S3
hierarchical nanostructure showed remarkable photocatalytic ac-
tivity and outperformed pure Bi2S3, indicating the potential appli-
cation in the degradation of organic dyes. Zhou et al. [430]
demonstrated the synthetic procedure and its mechanism for the
sphere organization of Bi2S3 nanorods follows as (a) mixed solution
of PEG and bismuth ions, (b) PEG coils and bismuth ions assembled
to Bi(III)-Tu-PEG globules, (c) The globules turn into flexible Bi2S3-
PEG nanorods based on sphere assembly after hydrothermal
treatment at 180  C for 1 h and (d) Bi2S3 nanorods assembled into a
microsphere after hydrothermal treatment at 180  C for 20 h and as
shown in Fig. 15.
In general, the photocatalytic activity of Bi2S3 catalysts strongly
depends on their extrinsic characteristics, such as morphology,
microstructure, particle size, and the surface properties were
characterized by various techniques. Recently, Wu et al. [378]
illustrated the TEM images of Bi2S3 nanocrystals prepared with a
Bi precursor concentration of 0.025 mol/L with Bi/S molar ratios of
(a) 1:0.5, (b) 1:1, (c) 1:1.5, and (d) 1:1.7 (Fig. 16) with different sizes
and shapes. Therefore, great efforts have been made to obtain Bi2S3
with different morphologies and structures, such as nanorods
[154], nanowires [155], and microstructures [156,157]. In particular,
97
heterojunction based Bi2S3/CdS NCs were constructed through an
easy wet chemistry approach and degradation mechanism of MB
was proposed [158]. Compared with the results indicated above
[153], the prepared heterostructure based Bi2S3 nanowire/CdS NPs
exhibited excellent photoactivity due to its microstructure. The
results encouraged us to tune the morphology of Bi2S3 for photo-
catalytic applications. Generally, Bi2S3 NSs can be used as a po-
tential visible-light photocatalyst through combination from other
semiconductors to form heterojunctions to improve light absorp-
tion and separation efficiency of photogenerated electronehole
pairs, such as CdS/Bi2S3, BiVO4/Bi2S3, Bi2S3/BiOBr, and so on. Lu et al.
[159] reported the preparation of a novel BiPO4/Bi2S3 hetero-
structure and their photocatalytic properties were evaluated by the
degradation of MB and RhB (concentration: 10 mg L
1) using 50 mg
of a catalyst under visible light.
Bi2S3 possessing a narrow band gap and considered a good
absorber in the whole visible region. Bi2S3 NPs are unstable, and
agglomeration readily occurs soon after formation, as a result sur-
face area reduces which decrease the adsorption power of catalyst.
The agglomeration can be reduced by several methods using
capping agents such as thioglycolic acid or by the use of dopants
such as TiO2 and BiOCl. Cao et al. investigated that the enhanced
photodegradation of RhB (concentration: 10 mg L
1) at pH 6.07 by
Bi2S3/BiOCl (surface area 15.44 m2 g
1) heterostructures [160]. Due
to narrow band gap, Bi2S3 (surface area 277.65 m2 g
1) didn't
98 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

Table 5
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based Ag2S NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

Ag2S/Ag3PO4 Xe-lamp 2.77 MO 464 10 ppm 100 [314]

Ag2S/TiO2 Hg-lamp 0.71 MO 462 20 mg/L 100 [315]
Ag2S QDs Hg-lamp 0.83 MO 462 20 mg/L 52 [315]
Ag2S/TiO2 Visible 0.71 MO 462 20 mg/L 69 [315]
Ag2S QDs Visible 0.83 MO 462 20 mg/L 47 [315]
Ag2S/TiO2 NIR 0.71 MO 462 20 mg/L 71 [315]
Ag2S QDs NIR 0.83 MO 462 20 mg/L 41 [315]
Ag2S/Co3O4 Solar 1.23 BG1 625 10 mg/L 99 [316]
Ag2S/ZnS Xe-lamp 1.4 MO 464 1.5  10
6 M 96 [317]
Ag2S/TiO2 Xe-lamp 1.1 MO 462.5 0.015 mM 90 [318]
Ag2S/TiO2 Xe-lamp 2.3 MB 663 5 mg/L 83.6 [319]
Ag2S/TiO2 Solar 1.95 RhB 554 1  10
5 M 99 [320]
Ag2S NPs Solar 1.95 RhB 554 1  10
5 M 70 [320]
Ag2S/ZnO NP UV 2.62 EBT 550 40 mg/L 69 [321]
Ag2S NPs Xe-lamp 3.92 RhB 554 10 mg/L 23 [322]
Ag2S/rGO Xe-lamp 3.86 RhB 554 10 mg/L 52 [322]
Ag2S/ZnS/GO Xe-lamp 3.81 RhB 554 10 mg/L 88 [322]
Ag2S NPs Xe-lamp 3.26 MB 664 100 mg/L 12 [150]
Ag2S/Ni NPs Xe-lamp 2.68 MB 664 100 mg/L 100 [150]
Ag2S/Ni/Ag3PO4 Xe-lamp 2.25 RhB 552 2 mg/L, pH ¼ 7 89.3 [323]
Ag2S/TiO2 LED 3.25 RhB 554 2  10
5 M 51 [324]
Ag2S/GR LED 2.6 RhB 554 2  10
5 M 86 [324]
Ag2S/TiO2/GR LED 3.3 RhB 554 2  10
5 M 90 [324]
Ag2S/ZnO Solar 2.9 RR 512, 285 2  10
4 M 98.9 [325]
Ag2S/ZnS Xe-lamp 3.2 MO 462 1  10
5 M 91 [326]
Ag2S/MCM-41 UV 1.05 MB 664 0.16e3.2 ppm 94 [327]
Ag2S/TiO2 Visible 1.95 MB 665 2  10
5 M 60 [328]
Ag2S MWCNTs Hg-lamp 1.11 MO 464 20 mg/L 100 [329]
Ag2S NPs Hg-lamp 1.11 MO 464 20 mg/L 78 [329]
Ag2S/Ag3PO4 Xe-lamp 1.01 RhB 553 1  10
5 M 100 [330]
Ag2S/CdS/ZnS Solar 2.73 CR 495 12 ppm 98 [331]
Ag2S/ZnS Solar 2.77 CR 495 12 ppm 68 [331]
Ag2S/CdS Solar 2.95 CR 495 12 ppm 74 [331]
Ag2S/TiO2 Xe-lamp 3.2 MO 462.5 0.015 mM 100 [332]
Ag2S MRs Solar 0.9 MO 463 1  10
6 M 99 [333]
Ag2S MRs Solar 0.9 MB 662 1  10
6 M 98.6 [333]
Ag2S MRs Solar 0.9 CV 438 1  10
6 M 98.8 [333]
Ag2S MRs Solar 0.9 R6G 528 1  10
6 M 98.4 [333]
Ag2S MRs Solar 0.9 SDI 514 1  10
6 M 99.9 [333]
Ag2S/Ag/Ag3CuS Xe-lamp 1.12 MO 464 10 mg/L 90.4 [334]
Ag2S NPs Visible 0.91 MB 663 5  10
5 M 42 [335]
Ag2S/C60 Visible 1.97 MB 663 5  10
5 M 100 [335]
Ag2S/CdS/MoS2 Xe-lamp 2.37 MB 664 5 mg/L 87 [336]
Ag2S/ZnS UV 2.55 MB 663 0.01 g/L 30 [337]
Ag2S/AgCl Hg-lamp 2.24 MO 462 25 g/L 99.98 [338]
Ag2S/CuS Xe-lamp 1.6 MO 464 20 mg/L 78.3 [339]
Ag2S/GR Xe-lamp 1.12 RhB 554 5 ppm 83 [340]
Ag2S/Ag2CO3 W-lamp 1.2 MO 464 0.02 g/L 95 [341]
Ag2S/TiO2 Visible 1.04 MO 462 1 mM 15 [342]
Ag2S/ZnO UV 2.9 AB1 320 2  10
4 M 100 [343]
Ag2S/NaNbO3 Visible 2.83 MB 664 1  10
5 M 95.5 [344]
Ag2S/AuAgS UV 1.6 RhB 554 2.5  10
2 M 84 [345]
Ag2S/Bi2WO6 Xe-lamp 2.68 RhB 553 1  10
5 M 84.6 [346]
Ag2S/Ag Visible 1.64 MO 464 20 mg/L 92.1 [347]
Ag2S NSs Xe-lamp 2.3 RhB 554 10 mg/L 62 [348]
Ag2S NPs UV 1.08 MB 664 0.32 ppm 41 [149]
Ag2S/MCM-41 UV 1.08 MB 664 0.32 ppm 94 [149]
Ag2S Solar 2.03 EY 516 1.5  10
5 M 72.51 [13]
Ag2S/SiO2 Solar 2.64 EY 516 1.5  10
5 M 91.24 [13]
Ag2S/TiO2 Solar 2.88 EY 516 1.5  10
5 M 96.41 [13]
Ag2S/SnS/ZnS Solar 3.33 CR 498 20 mg/L 97.2 [349]
Ag2S NPs Solar 1.1 FL 474 4  10
5 M 93 [350]

degrade RhB, and the degradation with BiOCl (surface area
73.88 m2 g
1) was not satisfactory i.e., only 45% degradation was
observed with BiOCl, but in combination they became efficient
photocatalysts and high efficiency up to 98% has been successfully
achieved. Liu et al. [366] reported the proposed mechanism for the
photocatalytic degradation of RhB over Bi2S3eZnS/graphene NCs
under visible-light irradiation (Fig. 17). Bi2S3 nanowire/CdS nano-
particles hetero-structure has the ability to degrade 98% of MR after
irradiation for just 40 min [161]. Wang et al. [162], performed that
the degradation experiments by Bi2S3 nanotubes incorporated with
carbon quantum dots for rapid degrading methylene blue (MB,
10 mg mL
1, 80 mL) and tetracycline hydrochloride (TC, 10 mg mL
1,
80 mL). The degradation efficiencies of MB (99%) and TC (78.1%)
were achieved in the subsequent 60 min of UV light using Bi2S3/C-
QDs. Long et al. [381] reported the photocatalytic degradation of
RhB by Bi2S3 and Bi2S3/MoS2 photocatalysts and results shown as
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 99

Fig. 15. Schematic illustration of the mechanism for the sphere organization of Bi2S3 nanorods, (a) Mixed solution of PEG and bismuth ions, (b) PEG coils and bismuth ions
assembled to Bi(III)-Tu-PEG globules, (c) The globules turn into flexible Bi2S3-PEG nanorods based on sphere assembly after hydrothermal treatment at 180  C for 1 h and (d) Bi2S3
nanorods assembled into a microsphere after hydrothermal treatment at 180  C for 20 h (Ref. [430]).

Fig. 16. (aed) TEM images of Bi2S3 nanocrystals prepared with a Bi precursor concentration of 0.025 mol/L with Bi/S molar ratios of (a) 1:0.5, (b) 1:1, (c) 1:1.5, and (d) 1:1.7
(Ref. [378]).

approximately 90% RhB degradation in Fig. 18. The photocatalytic 5.6. Doped and heterojunction based nanosized CoS photocatalysts
degradation of various dyes under different light irradiations using
doped and heterojunction based Bi2S3 NSs based heterogeneous CoS semiconductor nanostructures have received much atten-
photocatalysts is summarized in Table 6. tion due to their wide range of potential applications as optical and
100 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
Fig. 17. The proposed mechanism for the photocatalytic degradation of RhB over
Bi2S3eZnS/graphene nanocomposites under visible-light irradiation (Ref. [366]).
electronic devices, biological imaging, photocatalysts, light emit-
ting devices, gas sensors, and photovoltaic devices. In particular,
cobalt sulfides (CoS, CoS2, Co3S4, Co9S8, etc.) have attracted great
attention in light of their excellent optical, photocatalytic, electrical,
and magnetic properties and their applications for lithium-ion
batteries [163e166]. CoS, a significant binary compound semi-
conductor, has received great attention due to its unique charac-
teristics including narrow direct and indirect band gap, the high
absorption coefficient (104 cm
1) in sunlight, non-toxic and
abundant in nature, and also low-cost. Due to its proper band gap
and good adsorption properties, CoS can be used as a photocatalyst.
The photocatalytic treatment of organic dyes or compounds in
wastewater using CoS semiconductors has proven to be a prom-
ising green technology for environmental purification, as they
provide an interface with an aqueous medium and induce an
advanced oxidation process. Therefore, it is becoming a candidate
for future multifunctional devices and its applications. Gu et al.
[431] demonstrated the general schematic of the growth process of
graphene from graphene oxide wrapped CoS nanoparticles (Fig. 19).
The CoS should also be reasonable for structuring the
semiconductor-RGO hybrids for excellent photocatalytic activity.
Recently, H.Y. He reported the photocatalytic and the Fenton-like
photocatalytic degradation of malachite green dye (concentra-
tion: 5  10
6 M). It was degraded 96% in the water on the CoS NPs,
acting as a catalyst (50 mg) and hybrids [167].
Recently, Dong et al. [432] reported that the FESEM images of
the CoS products synthesized in a 10 mL aqueous solution con-
taining 0.17 mol L
1 of Co(NO3)2$6H2O and 0.17 mol L
1 of
Fig. 18. The photocatalytic degradation of rhodamine B (RhB) by different Bi2S3 photocatalysts (a) and the plot of (C/C0) against time (b) (Ref. [381]).
thiourea at 160  C for a given reaction time 2 he48 h (Fig. 20). The
prepared CoS are usually unstable and undergo aggregation soon
after formation, hence some reports of using CoS for slight pho-
todegradation of dyes appear until now. However, hybrid mate-
rials containing CoS are reported by one such group, comparing
the degradation of MB with CoS and their hybrids by incorpo-
rating CoS in AIMCM-41. In UVevis absorption spectra, CoS pro-
vides strong absorption edges at the wavelength of 320 and
350 nm, while CoS/AIMCM-41 has strong absorption edges at 290
and 360 nm. The redshift in case of CoS/AIMCM-41 favors
degradation of MB under the application of UV irradiation with
respect to CoS sample. On the other hand, shifting of absorption
edge from 320 nm for CoS bulk to 290 nm for CoS/AIMCM-41 was
observed. This blue shift as well as surface area, porosity and size
are attributed to enhance the photodegradation. Almost, 34% of
dye molecules were degraded after irradiating the sample for
70 min with CoS NPs (average size 25 nm), while 90% of the dye
molecules were decolorized and degraded with hybrid CoS/
AIMCM-41 (average size 8 nm) after exposing 0.32 ppm of sam-
ple at pH ¼ 2e12, for 60 min of irradiation under UV light. The
optimum pH at which the highest degradation was observed is at
pH ¼ 9 because the surface of a catalyst is negatively charged in
the basic medium, which favors degradation process [168].
Another group was reported that the degradation of MB and MR,
by CoS NPs doped PAN (Polyacrylonitrile) hybrid in a simple
photochemical reactor. The CoS/PAN hybrid provided a continual
decrease in characteristic absorbance peaks i.e., 663 nm for MB
and 430 nm for MR [169]. Xu et al. demonstrated the synthesized
CoS and Ag/CoS NPs used for the efficient photodegradation of MB
results as shown in Fig. 21 [393]. The doped and heterojunction
based CoS as heterogeneous photocatalysts exhibited efficient
photocatalytic degradation of various dyes under different light
irradiations is potted in Table 7.
5.7. Doped and heterojunction based nanosized FeS photocatalysts
FeS is used as a semiconductor material in photocatalysis and
solar cell applications because its absorption coefficient is much
higher than that of silicon, has an energy band gap (Eg ¼ 1.87 eV)
[170], and it is non-toxic, readily available, and cheap. Large surface
area of the catalyst is of prime concern for effective degradation of
organic dyes, which is associated with a small size of the catalyst
used for degradation process. Some of the research groups have
developed methods to synthesize FeS2 and FeS nanomaterials on a
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 101

Table 6
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based Bi2S3 NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

Bi2S3/Fe3O4 Xe-lamp 1.3 CR 496 30 mg/L 91.60 [351]

Bi2S3/Bi2MoO6 Xe-lamp 1.84 RhB 554 1  10
5 M 77.58 [352]
Bi2S3 NSs Xe-lamp 1.40 RhB 554 1  10
5 M 29.5 [352]
Bi2S3 NSs Visible 1.28 MB 663 10 mg/L 27.5 [353]
Bi2S3/TiO2 Visible 1.42 MB 663 10 mg/L 80 [353]
Bi2S3/TiO2/rGO Visible 1.46 MB 663 10 mg/L 97.8 [353]
Bi2S3 NSs Hg-lamp 1.91 RhB 554 20 mg/L 87 [354]
Bi2S3 NSs Hg-lamp 1.1 MO 462 10 mg/L 97 [153]
Bi2S3/MWCNT Visible 0.875 MB 664 15 mg/L 90.75 [355]
Bi2S3/WO3 W-lamp 1.9 RhB 553 10 mg/L 90.7 [356]
Bi2S3/TiO2 W-lamp 1.54 OG 478 10 mg/L 82 [357]
Bi2S3 NRs Hg-lamp 1.45 MB 664 50 mg/L 98 [358]
Bi2S3 NSs Hg-lamp 1.3 MO 462 50 ppm 18 [359]
Bi2S3/SnS2 Hg-lamp 1.5 MO 462 50 ppm 98.16 [359]
Bi2S3/Ag3PO4 LED 2.07 TB 665 25 mg/L 98.44 [360]
Bi2S3/Ag3PO4 LED 2.07 MO 470 25 mg/L 99.36 [360]
Bi2S3/Bi2O3 Xe-lamp 1.32 MO 465 20 mg/L 100 [361]
Bi2S3/Bi2WO6 Visible 2.38 RhB 554 1  10
5 M 77.2 [362]
Bi2S3 NPs Visible 1.40 RhB 554 1  10
5 M 18.4 [362]
Bi2S3/ZnS NPs UV 1.82 MB 664 5  10
5 M 82 [363]
Bi2S3 NPs UV 1.3 MB 664 5  10
5 M 58 [363]
Bi2S3/ZnS/TNF Hg-lamp 1.23 MB 664 6 ppm 100 [364]
Bi2S3/Bi2O3 Xe-lamp 2.28 RhB 554 5 mg/L 90.9 [365]
Bi2S3/ZnS Hg-lamp 1.71 RhB 552 1  10
5 M 72 [366]
Bi2S3/ZnS Hg-lamp 1.71 MB 665 1  10
5 M 65 [366]
Bi2S3/RGO Visible 1.54 MG 622 5 mg/L 99 [367]
Bi2S3 NPs Visible 1.4 MG 622 5 mg/L 60 [367]
Bi2S3 NPs W-lamp 1.48 MB 664 2  10
5 M 98 [368]
Bi2S3 NRs Xe-lamp 1.3 RhB 554 1  10
5 M 99 [369]
Bi2S3/MoS2 Xe-lamp 1.77 PR 446 100 ppm 83.4 [370]
Bi2S3 Xe-lamp 1.37 PR 446 100 ppm 41.4 [370]
Bi2S3/Bi2O2CO3 Xe-lamp 0.89 RhB 553 1  10
5 M 100 [371]
Bi2S3/ZnO UV-A 1.12 AB1 320 180 ppm 96 [372]
Bi2S3 NPs UV-A 1.3 AB1 320 180 ppm 68 [372]
Bi2S3/ZnS W-lamp 1.39 RhB 552 10 mg/L 87.50 [373]
Bi2S3 NPs W-lamp 1.39 RhB 552 10 mg/L 6.86 [373]
Bi2S3/BiVO4 Xe-lamp 2.71 RhB 553 1  10
5 M 98 [374]
Bi2S3/BiOI Xe-lamp 1.72 MO 464 10 mg/L 89.7 [375]
Bi2S3/Au Visible 1.4 MB 660 10 ppm 80 [376]
Bi2S3/CdS UV 1.43 MR 430 0.01 g/L 90 [161]
Bi2S3/CdS UV 1.43 MR 430 0.01 g/L 98 [161]
Bi2S3 NWs UV 1.43 MR 430 0.01 g/L 51 [161]
Bi2S3/TiO2 UV 2.46 MG 622 5  10
6 M 90 [377]
Bi2S3 NSs UV 1.31 MO 462 20 mg/L 70 [378]
Bi2S3 NSs UV 1.31 MB 663 20 mg/L 72 [378]
Bi2S3 NSs UV 1.31 RhB 553 20 mg/L 100 [378]
Bi2S3/CdS/TiO2 Xe-lamp 2.1 RhB 554 1  10
5 M 100 [379]
Bi2S3/CdS/TiO2 Xe-lamp 2.1 MO 464 1  10
5 M 100 [379]
Bi2S3/Fe3O4 Hg-lamp 2.6 RhB 554 5 mg/L 100 [380]
Bi2S3/MoS2 Xe-lamp 1.3 RhB 553 5 mg/L 91 [381]
Bi2S3 Xe-lamp 1.3 RhB 553 5 mg/L 51 [381]
Bi2S3/CuS Visible 1.8 RhB 554 1 g/L 55 [382]
Bi2S3 Visible 1.34 RhB 554 1 g/L 12 [382]
Bi2S3/BiPO4 Visible 3.81 MB 664 10 mg/L 80 [383]
Bi2S3/SnS2 Xe-lamp 2.75 RhB 553 0.02 mmol/L 98.4 [383]
Bi2S3/BiOBr Xe-lamp 2.8 RhB 553 50 mg/L 98.6 [384]
Bi2S3/(BiO)2CO3 Visible 1.39 RhB 554 5 mg/L 92 [385]
Bi2S3/TiO2 Xe-lamp 1.3 MO 465 20 mg/L 98 [386]
BiVO4/Bi2S3/MoS2 Solar 1.2 RhB 552 10 mg/L 97 [387]
BiVO4/Bi2S3/MoS2 Solar 1.2 MB 662 10 mg/L 93 [387]
BiVO4/Bi2S3/MoS2 Solar 1.2 MG 625 10 mg/L 94 [387]
Bi2S3/CuS Xe-lamp 1.6 RhB 553 2  10
5 M 100 [388]

Fig. 19. The schematic representation of the growth process of graphene wrapped CoS nanoparticles (Ref. [431]).
102 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

Fig. 20. FESEM images of the CoS products synthesized in a 10 mL aqueous solution containing 0.17 mol L
1 Co(NO3)2$6H2O and 0.17 mol L
1 thiourea at 160  C for a given reaction
time: (a) 2 h, (b) 5 h, (c) 12 h, (d)24 h, (e) 36 h, (f) 48 h (Ref. [432]).

Fig. 21. (a) The photodegradation of MB over CoS and Ag/CoS samples in dark (a) and (b) in light, (c) kinetic curves for the MB photodegradation with pure CoS and Ag/CoS samples;
(d) the comparison of reaction rate constant, k, obtained from linear fitting (Ref. [393]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 103
Table 7
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based CoS NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

Co3S4 Hg-lamp 1.62 RhB 553 1  10
4 M 85 [389]

Co3S4/Fe Hg-lamp 1.62 RhB 553 1  10
4 M 95 [389]
Co3S4 Hg-lamp 1.62 MG 621 1  10
4 M 89 [389]
CoS/rGO Solar 1.15 MG 621 5  10
6 M 96 [167]
Co3S4/Ag2S Xe-lamp 1.7 MB 665 100 mg/L 97 [390]
Co3S4/Ag2S Xe-lamp 1.7 MO 465 100 mg/L 98 [390]
CoS/MCM-41 W-lamp 1.8 MB 664 0.25e3.2 ppm 98 [391]
CoS/Au NCs US 1.6 R6G 528 1  10
5 M 87 [392]
CoS/Ag NCs Visible 1.82 MB 663 10 mg/L 72.65 [393]
CoS/AIMCM-41 W-lamp 1.8 BB9 664 0.25e3.2 ppm 98 [394]
CoS Xe-lamp 1.24 MB 664 10 mg/L 54.4 [395]
CoS/GNS Xe-lamp 1.24 MB 664 10 mg/L 91.9 [395]
CoS/ZnS W-lamp 1.91 RB 550 1  10
3 M 32 [396]
CoS NPs Hg-lamp 1.10 MB 664 0.25 ppm 90 [168]
CoS/AIMCS41 Hg-lamp 1.12 MB 664 100 mg/L 90 [168]
CoS2/TiO2 Xe-lamp 1.32 RBB 597 3  10
6 M 89 [168]
CoS2/rGO Solar 1.2 MG 662 5  10
6 M 98 [397]
CoS/PAN Hg-lamp 2.66 MR 430 100 mg/L 90 [169]
Co2.67S4 Xe-lamp 0.92 MB 664 10 mg/L 84 [398]

Fig. 22. The synthesis process of FeS/ZnO nanoarrays on a steel screen (Ref. [403]).

Fig. 23. TEM images and in inset Live FFT of FeS NPs obtained from (a) EG, (b) EN and (c) NH3. SAED patterns of FeS NPs obtained from (d) EG, (e) EN and (f) NH3 (Ref. [407]).
104 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

Fig. 24. (a) Time dependent absorbance spectral change of aqueous solution of MB (1.65  10
5 M) catalyzed by 20 mg FeS NPs (obtained from EG) under light irradiation for
195 min. (b) Degradation of MB solution (i) without catalyst in dark, (ii) FeS from EG in dark, (iii) without catalyst in light, (iv) TiO2 in light (v) FeS from EG in light, (vi) FeS from EN
in light, and (vii) FeS from NH3 in light. Inset: kinetic plots for the photodegradation process of MB by (i) FeS from EG in light, (ii) FeS from EN in light, and (iii) FeS from NH3 in light
(Ref. [407]).

Table 8
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based FeS, and FeS2 NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

FeS2 NRs LED-lamp 1.24 MB 664 15 mg/L 95 [399]

FeS2 NCs Xe-lamp 0.95 MO 463 30 mg/L 80 [400]
FeS NPs W-lamp 2.43 RB 553 6.6  10
5 M 97 [174]
FeS NPs W-lamp 2.43 MB 653 6  10
6 M 98 [174]
FeS2 NPs Visible 2.4 MB 664 10 mg/L 13.2 [173]
FeS2/Co Visible 2.12 MB 664 10 mg/L 48.9 [173]
FeS2 NTs Xe-lamp 1.69 MB 663 5 mg/L 75 [401]
FeS2 NPs Visible 1.3 MB 664 1 mg/L 95.9 [402]
FeS2 NPs Visible 1.3 SY 416 1 mg/L 99.29 [402]
FeS/ZnO Xe-lamp 2.65 MB 660 5 mg/L 97 [403]
FeS2 NSs Visible 2.17 MO 464 1 mg/L 93.09 [404]
FeS2 NSs Visible 2.17 NYH 428 1 mg/L 98.15 [404]
FeS2 NPs Visible 1.9 MB 650 10 mg/L 95 [405]
FeS2 films W-lamp 2.7 RhB 546 6.6  10
6 M 84 [171]
FeS/SnO2 W-lamp 1.98 ARS 540 50 ppm 90 [406]
FeS/SnO2 W-lamp 1.98 MB 660 50 ppm 94 [406]
FeS/SnO2 W-lamp 1.98 RhB 539 50 ppm 98 [406]
FeS NPs W-lamp 3.13 MB 663 1.65  10
5 M 99.35 [407]
FeS2 NPs UV 0.95 MB 662 1  10
5 M 99.2 [408]
FeS2 NPs UV 0.95 ST 518 1  10
5 M 99.5 [408]
FeS2 NPs UV 0.95 MO 462 1  10
5 M 87.9 [408]
FeS2 NPs UV 0.95 RhB 554 1  10
5 M 97 [408]
FeS2 NPs UV 0.95 PB 638 1  10
5 M 97.9 [408]

Fig. 25. The synthetic scheme for the formation of uncapped cubic and MCE-capped dendritic PbS microstructures (Ref. [185]).
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 105

steel screen and as shown in Fig. 22 [403]. Maji et al. [407]
described TEM images and in inset Live FFT of FeS NPs obtained
from different solvents and SAED patterns of FeS NPs (Fig. 23). In
addition, it reported the photodegradation of MB dye using FeS NPs
with different solvents under W-lamp results 99% degradation of
MB and as shown in Fig. 24. Bhar et al. [171] investigated the
photocatalytic activity of FeS2 thin films by measuring the decrease
in absorption peak maxima of an aqueous solution of 20 ppm Rose
Bengal (RB) dye at 546 nm. The photocatalytic degradation of RB
dye using nano FeS2 thin film exposed to 100 W clear glass tungsten
lamp (Philips) was compared to light (without FeS2 film) and dark
reactions (with FeS2 film). It is evident that in presence of both light
and catalyst (FeS2 thin film), about 84% degradation of RB dye so-
lution was achieved after 300 min of exposure. These mesoporous
FeS2 NPs were characterized with an average diameter of 40.33 Å
having the high surface area of 49.53 m2 g
1, which greatly

Fig. 26. (aed, above) SEM and (aed, below) TEM images of PbS nanoparticles (Ref. [186]).
106 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
Fig. 27. The electron transfer model for the high photocatalytic activity and stability of
SnO2ePbS nanocomposites (Ref. [410]).
enhances the adsorption of dye over the catalyst which in turn
enhances degradation process.
FeS2 was reported that pyrite also can be applied as a UV-light-
induced photocatalyst, but its performance was not good [172] but
few reports focused on its visible-light-driven photocatalytic per-
formance. Long et al. [173] investigated the photocatalytic activities
of the FeS2 NPs (0.05 g), determined by the degradation of MB
(concentration: 10 mg/L) under visible-light irradiation at ambient
temperature. The Co-doped FeS2 samples exhibited higher photo-
degradation efficiency than that of the pristine FeS2 and the Co/FeS2
samples that showed the highest photodegradation efficiency. After
210 min irradiation, the Co/FeS2 sample degraded 48.9% of MB,
which was 36.5% more than that of the pristine FeS2. Dutta et al.
Fig. 28. (a) Time-dependent UVeVis absorption spectra for degradation of MO using PbS microstructures (25 mg S2) (a) and S7 (b) under UV light, (c) percentage conversion of MO
with time (d) plot of ln(C0/C) with time (Ref. [185]).
[174], reported similar results for RB and MB degradation using FeS2
NPs. The enhanced photodegradation of dyes with FeS2 NPs was
evaluated with the help of UV-spectrophotometer from 400 to
600 nm for RB (initial concentration 6.6  10
5 M) and
600e750 nm for MB (initial concentration 6  10
6 M), by exposing
aqueous solutions to incandescent tungsten halogen lamp (200 W),
sharp decrease in the absorption maxima for both dyes was
observed with passage of irradiation time. Similarly, the photo-
catalytic degradation of various dyes under different light irradia-
tions using some of the doped and heterojunction based iron
sulfide NPs as heterogeneous photocatalysts is summarized in
Table 8.
5.8. Doped and heterojunction based nanosized PbS photocatalysts
PbS NSs are prime candidates for use as sunlight absorbers in
sensitized solar cells because of their size-dependent band gap, and
thus have widely tunable absorption properties, combined with
simple, low-cost fabrication procedures. PbS is an important binary
IVeVI semiconductor with a rather small band gap (0.41 eV) and
large exciton Bohr radius (18 nm) [175e177], and it has been widely
used in photocatalysis, which exhibits high photocatalytic activity
under visible light irradiation. Due to its unique photoconductive
properties, PbS is applied as an infrared detector for mid-infrared
lasers, promising photosensitive material and is a good photo-
catalyst [178]. Consequently, PbS nanocrystals and nanowires are
potentially useful in electroluminescent devices such as light-
emitting diodes. Quantum-sized PbS NPs may have applications
in light-emitting diodes and high-speed switching, IR detectors.
The drawback of PbS is that it is insufficiently stable for catalysis, at
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 107

Table 9
The summary of studies on photocatalytic degradation of dyes in the presence of doped and heterojunction based PbS NSs as photocatalysts.

Sample Light source Band gap, eV Dye Wavelength, nm Concentration of dye % of Degradation Ref.

PbS/TiO2 UV 2.3 MO 465 10 ppm 98 [409]

PbS/SnO2 Xe-lamp 0.56 RhB 555 1  10
5 M 84 [410]
PbS/TiO2 Solar 2.8 MO 464 5  10
5 M 72.44 [411]
PbS-STN Xe-lamp 1.6 MO 464 0.4 mg/L 95 [412]
PbS/TNT Hg-lamp 2.9 MB 660 25 ppm 99 [413]
PbS/TNT Hg-lamp 2.9 MG 657 25 ppm 71 [413]
PbS/TNT Hg-lamp 2.9 RhB 554 25 ppm 94 [413]
PbS/TNT Hg-lamp 2.9 RB 549 25 ppm 99.2 [413]
PbS/TNT Hg-lamp 2.9 IC 610 25 ppm 95 [413]
PbS/TiO2 Xe-lamp 0.8e3.2 ARD 507 1000 mg/L 78 [414]
PbS/B/N/TiO2 Xe-lamp 0.8e3.2 ARD 507 1000 mg/L 95 [414]
PbS/MoS2 NCs W-lamp 3.23 MB 662 0.3 mM 83 [415]
PbS/PVDF-gMAH Xe-lamp 1.2 MB 664 15 ppm 90 [416]
PbS/CdS Hg-lamp 2.6 MO 464 35 g/L 81 [417]
PbS/Fe3O4 UV 0.3e5.2 A Black 620 25 ppm 95 [418]
PbS/Fe3O4 UV 0.3e5.2 A Brown 465 25 ppm 75 [418]
PbS/Fe3O4 UV 0.3e5.2 A Violet 520 25 ppm 80 [418]
PbS/Fe3O4 UV 0.3e5.2 A Blue 630 25 ppm 85 [418]
PbS/K4Nb6O17 UV 0.41 RhB 554 10 mM 71.1 [419]
PbS/GR/TiO2 Visible 1.94 MB 663 1  10
4 M 41 [420]
PbS/GR Visible 0.41 MB 663 1  10
4 M 20 [420]
PbS NDs Xe-lamp 0.41 RhB 554 5  10
6 M 86 [186]
PbS/CdS/Ti6O13 Solar 2.93 RB5 600 40 mg/L 100 [421]
PbS/ZnO Visible 1.2e1.5 MO 464 10 mg/L 48 [422]
PbS/ZnO/CdS Visible 1.2e2.3 MO 464 10 mg/L 83 [422]
PbS/TiO2/ITO Hg-lamp 3.2 MO 464 15 ppm 96.30 [423]
PbS/TiO2/CdS/ITO Hg-lamp 3.22 MO 464 15 ppm 97.21 [423]
PbS/BiOBr Visible 1.54 RhB 554 10 m M 99.5 [424]
PbS Visible 0.61 RhB 554 10 m M 28 [424]

least in aqueous media as it readily undergoes photocorrosion
[179]. However, PbS is prone to photocorrosion in photocatalytic
reactions, and the rapid recombination rate of the excited electro-
nehole pairs partly limits its photocatalytic activity. Among various
methods, coupling PbS with another wide-band-gap semi-
conductor is a good choice [180].
Recently, different morphologies of PbS nanocrystals have been
prepared such as nanotubes, nanoflowers, nanostars, nanowires,
matchstick and dendrites [181,182]. In general, the formation of
these morphologies are assisted by templates/capping agents [183].
On the other hand, detailed investigations on morphological evo-
lution of PbS nanocrystals formed in the absence of templates/
capping agents are rare [184]. Kaur et al. [185] reported the syn-
thesis scheme for the formation of uncapped cubic and MCE-
capped dendritic PbS microstructures (Fig. 25) and morphology
dependent photocatalytic investigation of both cubic and dendritic
PbS structures, for degradation of MO dye under UV-light irradia-
tion; revealed higher photocatalytic activity of PbS as compared to
that of other precursor capped PbS. The prepared sample of PbS
microstructures (25 mg) was suspended in a solution of MO (con-
centration: 2  10
5 M) in 40 ml of H2O in a quartz tube at ambient
temperature. As it can be seen, with an increase in irradiation time
the concentration of MO decreases, and at the end of 180 min, the
degradation of MO was found to be 79.78% and 95.41%, catalyzed by
cubic and dendritic PbS microstructures respectively, indicating
relatively higher photocatalytic performance of dendrites over
cubes and as shown in Fig. 28. Wu et al. [186] reported the SEM and
TEM images of the synthesized PbS NPs (Fig. 26) and its photo-
catalytic property of PbS dendrites (50 mg). It was found that the
novel nanocrystals have high catalytic efficiency for the degrada-
tion of RhB (concentration: 5  10
6 M) is 90% under 4 h visible
irradiation. Kar et al. [410] represented the schematic model for the
high photocatalytic activity and stability of SnO2ePbS nano-
composites (Fig. 27). It explains the electron transfer from the CB of
PbS to CB of SnO2 for the degradation of RhB using PbS/SnO2
nanocomposites. The photocatalytic degradation efficiencies of
doped and heterojunction based PbS NSs as heterogeneous pho-
tocatalysts for the enhancement degradation of various dyes under
different light irradiations is listed in Table 9.
6. Conclusions
Recent developments in technology allow us to fabricate
different semiconductors with large surface area and different
surface functionalities for successful removal of toxic dyes. In this
regard, we have discussed the recent research improvements tar-
geting the degradation or removal of different dyes by using various
semiconductor MSNSs as potential photocatalysts. These materials
are modified with different functionalities such as dopants and
heterostructures are prepared with improved photocatalytic ac-
tivity. Since the scopes of metal sulphide-based photocatalysts
were broad, some of the catalysts based on ZnS, CdS, CuS, Ag2S,
Bi2S3, CoS, FeS2 and PbS etc. were reviewed in this paper. We have
discussed in detail, the effect of adsorption power of different dyes,
relative percentage degradation, particle size, morphology, light
sources, reaction time and concentration of dyes. It demonstrates
the principle of photocatalysis lends itself nicely to such different
targets as converting solar energy into storable chemical energy
and catalyzing chemical reactions in the synthesis and degradation
of dyes for environmental safety. Applications of photocatalysis are
not limited to dyes and are indeed extended to organic molecules,
inorganic compounds, industrial pollutants, pesticides, in-
secticides, phenols, and substituted organic compounds etc. The
efficient photocatalytic activity of reviewed semiconductor MSNSs
is useful photocatalytic material for industrial effluent treatment
because of its advantages, including effortlessness, low-cost, reus-
ability, and favorable performance.
7. Future aspects
Recently, a few efforts have been made for the synthesis of high
surface area, particular shape and size of the materials by
108 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113

incorporation of MSNSs photocatalytic materials in or on the sur- TNF Titanium nanoflakes

face of high surface area materials like zeolites, clay, silica and ITO Indium-doped tin oxide
metal-organic framework. The advantages of these materials are UV Ultra violet
that they can be easily separated from the treated water and the Vis Visible
dangerous effect of contamination due to nanomaterials in water NIR Near Infra Red
can be avoided. Due to the synergic effect of adsorption, photo- Xe Xenon lamp
catalytic degradation efficiency of dyes may get enhanced. The W Tungsten lamp
separated photocatalytic materials can easily be regenerated, which Hg Mercury lamp
reduces the cost of regeneration due to electrical energy. In addi- LED Light Emitting Diode
tion, the photostability will be one main challenge for photocatalyst NSs Nanostructures
development. A photocatalyst with very high efficiency is still NPs Nanoparticles
useless if the lifetime of the catalyst is too short. For majority sys- NRs Nanorods
tems, chemical corrosion and/or photodegradation of photo- NFs Nanoflakes/films
catalysts are difficult to avoid. The extended photocatalyst stability NCs Nanocomposites
has only been achieved in a few examples to date, which however NWs Nanowires
often requires highly complicated synthetic processes. To develop a NTs Nanotubes
stable photocatalytic system with high efficiency and low-cost will NDs Nanodimensions
be the central task to realize a practically viable photocatalyst for QDs Quantum Dots
solar fuel production for fields related to energy and environment MWCNTs Multi Wall Carbon Nanotubes
from scientific and engineering viewpoints. MRs Microribbons
VB Valence band
Conflict of interest CB Conduction band
Eg Band gap
The authors declare no conflict of interests. HOMO Highest Occupied Molecular Orbital
LUMO Lowest Unoccupied Molecular Orbital
Acknowledgements MB Methylene Blue
MR Methyl Red
One of the authors, Dasari Ayodhya gratefully acknowledges MO Methyl Orange
UGC, New Delhi, India, for the award of Senior Research Fellowship. MG Malachite Green
The authors would like to thank DST-FIST, New Delhi, India for MV Methyl Violet
providing necessary analytical facilities and sincere thanks to the BB Basic dye (Metaphenylene blue)
Head, Department of Chemistry, Osmania University for providing BG Brilliant Green
infrastructure and other necessary facilities. RhB Rhodamine B
RB6G Rhodamine 6G
Abbreviations RB Rose Bengal
EY Eosin Y
MSNSs Metal sulfide nanostructures CR Congo Red
ZnS Zinc sulfide CV Crystal Violet
CdS Cadmium sulfide SO Safranin O
CuS Copper sulfide ST Safranin T
Ag2S Silver sulfide FL Fluorescein
Bi2S3 Bismuth sulfide XO Xylenol Orange
CoS Cobalt sulfide OG Orange Gelb (Azo dye)
FeS2 Iron sulfide IC Indigo Carmine
PbS Lead sulfide TB Toluidine blue
TiO2 Titanium dioxide PR Phenol Red
SiO2 Silicon dioxide PB Patent blue
RGO Reduced graphene oxide ARS Alizarin Red S
RG Reduced Graphene SDI Sudan I
BiOCl Bismuthoxychloride EB Evans Blue
PANI Polyaniline EBT Eriochrome Black T
PAN Polyacetonitrile RBB Reactive black B
SnO2 Tin oxide AZ Alizarin
SnS Tin sulfide AB29 Acid blue 29
PEG Polyethylene glycol RR43 Reactive Red 43
TGA Thioglycolic acid AO7 Acid orange 7
Fe2O3 Ferric oxide SY Solvent Yellow 33
MoS2 Molybdenum sulphide NYH Novacron yellow Huntsman
C3N4 Carbon nitride ARD Amine reactive dye
ZnO Zinc oxide TC Tetracycline hydrochloride
WO3 Tungsten oxide US Ultrasound
Ag3PO4 Silver phosphate eV electron volt
Co3O4 Cobalt oxide nm nanometer
C60 Fullerenes mg milligrams
TNT Titanium nanotubes g grams
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113 109

mL milliliter [43] S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, Ultrason.

Sonochem. 42 (2018) 171e182.
mM millimolar
[44] S. Zinatloo-Ajabshir, Z. Zinatloo-Ajabshir, M. Salavati-Niasari, S. Bagheri,
M Molar S.B. Hamid, J. Energy Chem. 26 (2017) 315e323.
Ppm parts per million [45] S. Zinatloo-Ajabshir, M. Salavati-Niasari, Z. Zinatloo-Ajabshir, Sep. Purif.
Technol. 177 (2017) 110e120.
[46] P.A. Reddy, S.P. Vattikuti, M.K. Kumar, C. Manvitha, M.P. Sharma, V.D. Kumari,
References C. Byon, Ceramics Int. (2018), https://doi.org/10.1016/j.ceramint.2018.03.262.
[47] M. Chincholi, P. Sagwekar, C. Nagaria, S. Kulkarni, S. Dhokpande, Int. J. Sci.
[1] A. Albini, M. Fagnoni, Chem. Sus. Chem. 1 (2008) 63e66. Eng. Technol. Res. 3 (2014) 835e840.
[2] A. Fujishima, K. Honda, Nature 238 (1972) 37e38. [48] M.T. Yagub, T.K. Sen, S. Afroze, H.M. Ang, Adv. Colloid Interface 209 (2014)
[3] J.A. Turner, Science 305 (2004) 972e974. 172e184.
[4] N. Serpone, E. Pelizzetti, Photocatalysis: Fundamentals and Applications, [49] M.S. Chiou, P.Y. Ho, H.Y. Li, J. Dyes Pigments 60 (2004) 69e84.
Wiley-Interscience, New York, 1989. [50] D.M. Indra, C.S. Vimal, K.A. Nitin, M.M. Indra, Colloids Surf. A 264 (2005)
[5] C. Beer, R. Foldbjerg, Y. Hayashi, D.S. Sutherland, H. Autrup, Toxicol. Lett. 208 17e28.
(2012) 286e292. [51] R. Qadeer, Colloids Surf. A 293 (2007) 217e223.
[6] S. Wagner, J. Bloh, C. Kasper, D. Bahnemann, Green 1 (2011) 171e188. [52] A.K.A. Rathi, S.A. Puranik, Am. Dye Stuff Rep. 88 (1999) 42e50.
[7] C. Byrne, G. Subramanian, S.C. Pillai, J. Environ. Chem. Eng. (2017), https:// [53] E.A. Clarke, R. Anliker, Organic dyes and pigments, in: Anthropogenic Com-
doi.org/10.1016/j.jece.2017.07.080. pounds, Springer, Berlin Heidelberg, 1980, pp. 181e215.
[8] A.A. Alshatwi, P.V. Subbarayan, E. Ramesh, A.A. Al-Hazzani, M.A. Alsaif, [54] A. Demirbas, J. Hazard. Mater. 167 (2009) 1e9.
A.A. Alwarthan, Food Addit. Contam. Part A 30 (2013) 1e10. [55] G. Mishra, M. Tripathy, Colourage 40 (1993) 35e38.
[9] E. Radziun, J.D. Wilczynska, I. Ksiazek, K. Nowak, E.L. Anuszewska, A. Kunicki, [56] W.K. Walthall, J.D. Stark, Environ. Pollut. 104 (1999) 207e215.
A. Olszyna, T. Zabkowski, Toxicol. In Vitro 25 (2011) 1694e1700. [57] S. Tsuda, M. Murakami, N. Matsusaka, K. Kano, K. Taniguchi, Y.F. Sasaki,
[10] J. Sun, S. Wang, D. Zhao, F.H. Hun, L. Weng, H. Liu, Cell Biol. Toxicol. 27 (2011) Toxicol. Sci. 61 (2001) 92e99.
333e342. [58] G.M. Shaul, T.J. Holdsworth, C.R. Dempsey, K.A. Dostal, Chemosphere 22
[11] B. Ohtani, New and Future Developments in Catalysis: Chapter 5: Principle of (1991) 107e119.
Photocatalysis and Design of Active Photocatalysts, Elsevier Inc, 2013, [59] O. Tünay, I. Kabdasli, G. Eremektar, D. Orhon, Water Sci. Technol. 34 (1996) 9e16.
pp. 121e144. [60] M.A. Fox, M.T. Dulay, Chem. Rev. 93 (1993) 341e357.
[12] Y.F. Pan, G.S. Wang, L. Liu, L. Guo, S.H. Yu, Nano Res. 10 (2017) 284e294. [61] X. Li, J. Yu, M. Jaroniec, Chem. Soc. Rev. 45 (2016) 2603e2636.
[13] D. Ayodhya, G. Veerabhadram, J. Environ. Chem. Eng. 6 (2018) 311e324. [62] T.S. Natarajan, K. Natarajan, H.C. Bajaj, R.J. Tayade, J. Nanopart. Res. 15 (2013)
[14] A.P. Alivisatos, Science 271 (1996) 933e937. 1669.
[15] N. Tsolekile, S. Parani, M.C. Matoetoe, S.P. Songca, O.S. Oluwafemi, Nano- [63] V. Etacheri, C.D. Valentin, J. Schneider, D. Bahnemann, S.C. Pillai,
Struct. Nano-Objects 12 (2017) 46e56. J. Photochem. Photobiol. C 25 (2015) 1e29.
[16] Y. Zhang, H. Xu, Q. Wang, Chem. Commun. 46 (2010) 8941e8943. [64] Z.M. Abou-Gamra, M.A. Ahmed, J. Photochem. Photobiol. B 160 (2016)
[17] Y. Zhang, J. Lu, S. Shen, H. Xu, Q. Wang, Chem. Commun. 47 (2011) 134e141.
5226e5228. [65] F. Wu, W. Liu, J. Qiu, J. Li, W. Zhou, Y. Fang, S. Zhang, X. Li, Appl. Surf. Sci. 358
[18] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahenemann, Chem. Rev. 95 (2015) 425e435.
(1995) 69e96. [66] H.A. Hamad, W.A. Sadik, M.M. Abd El-latif, A.B. Kashyout, M.Y. Feteha,
[19] W.Z. Tang, H. An, Chemosphere 31 (1995) 4171e4183. J. Environ. Sci. 43 (2016) 26e39.
[20] D. Ayodhya, G. Veerabhadram, J. Photochem. Photobiol. A Chem. 356 (2018) [67] S. Anandan, M. Yoon, J. Photochem. Photobiol. C 4 (2003) 5e18.
545e555. [68] A. Corma, H. Garcia, Chem. Commun. 13 (2004) 1443e1459.
[21] U.I. Gaya, A.H. Abdullah, J. Photochem. Photobiol. C Reviews 9 (2008) 1e12. [69] W.Z. Tang, H. An, Chemosphere 31 (1995) 4157e4170.
[22] C.B. Ong, L.Y. Ng, A.W. Mohammad, Renew. Sustain. Energy Rev. 81 (2018) [70] V. Meshko, L. Markovska, M. Mincheva, A.E. Rodrigues, Wat. Res. 35 (2001)
536e551. 3357e3366.
[23] V. Iliev, D. Tomova, L. Bilyarska, J. Photochem. Photobiol. A Chem. 351 (2018) [71] W.S. Kuo, P.H. Ho, Chemosphere 45 (2001) 77e83.
69e77. [72] C. Galindo, P. Jacques, A. Kalt, Chemosphere 45 (2001) 997e1005.
[24] S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M.J. Salavati-Niasari, Mater. Sci. [73] P. Cooper, Colour Technol. 109 (1993) 97e100.
Mater. Electron. 28 (2017) 17849e17859. [74] S.S. Patil, V.M. Shinde, Environ. Sci. Technol. 22 (1988) 1160e1165.
[25] S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, J. Mol. Liq. [75] A.T. Moore, A. Vira, S. Fogel, Environ. Sci. Technol. 23 (1989) 403e406.
234 (2017) 430e436. [76] M.C. Venceslau, S. Tom, J.J. Simon, Environ. Technol. 15 (1994) 917.
[26] M.S. Morassaei, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Adv. Powder [77] I. Arslan, I.A. Balcioglou, Dyes Pigments 43 (1999) 95e108.
Technol. 28 (2017) 697e705. [78] W.Z. Tang, Z. Zhang, H. An, M.O. Quintana, D.F. Torres, Environ. Technol. 18
[27] M.S. Morassaei, S. Zinatloo-Ajabshir, M.J. Salavati-Niasari, Mater. Sci. Mater. (1997) 1e12.
Electron. 27 (2016) 11698e11706. [79] X. Li, F. Li, Environ. Sci. Technol. 35 (2001) 2381e2387.
[28] S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mol. Liq. 243 (2017) 219e226. [80] M. Stylidi, D.I. Kondarides, X.E. Verykios, Appl. Catal. B 40 (2003) 271e286.
[29] E.R. Svirbutaviciene, A. Neagu, V. Vickackaite, V. Jasulaitiene, A. Zarkov, [81] K. Tanaka, K. Padermpole, T. Hisanaga, Water Res. 34 (2000) 327e333.
C.W. Tai, A. Katelnikovas, J. Photochem. Photobiol. A Chem. 351 (2018) [82] H. Lachheb, E. Puzenat, A. Houas, M. Ksibi, E. Elaloui, C. Guillard,
29e41. J.M. Herrmann, Appl. Catal. B 39 (2002) 75e90.
[30] S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, Ultrason. [83] O. Carp, C.L. Huisman, A. Reller, Prog. Solid State Chem. 32 (2004) 33e177.
Sonochem. 39 (2017) 452e460. [84] V. Augugliaro, M. Litter, L. Palmisano, J. Soria, J. Photochem. Photobiol. C 7
[31] S. Mortazavi-Derazkola, S. Zinatloo-Ajabshir, M. Salavati-Niasari, Adv. Pow- (2006) 127e144.
der Technol. 28 (2017) 747e754. [85] X. Yang, H. Yu, X. Guo, Q. Ding, T. Pullerits, R. Wang, G. Zhang, W. Liang,
[32] S. Zinatloo-Ajabshir, S. Mortazavi-Derazkola, M. Salavati-Niasari, Int. J. M. Sun, Mater. Today Energy 5 (2017) 72e78.
Hydrogen Energy 42 (2017) 15178e15188. [86] P. Pizarro, C. Guillard, N. Perol, J.M. Herrmann, Catal. Today 101 (2005)
[33] S. Mortazavi-Derazkola, S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mater. Sci. 211e218.
Mater. Electron. 28 (2017) 1914e1924. [87] H. Yates, M. Nolan, D. Sheel, M. Pemble, J. Photochem. Photobiol. A 179
[34] S. Zinatloo-Ajabshir, Z. Salehi, M. Salavati-Niasari, Ceramics Int. 44 (2018) (2006) 213e223.
3873e3883. [88] S. Challagulla, R. Nagarjuna, R. Ganesan, S. Roy, Nano-Struct. Nano-Objects 12
[35] Z. Salehi, S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mol. Liq. 222 (2016) (2017) 147e156.
218e224. [89] A. Arques, A.M. Amat, L. Santos-Juanes, R.F. Vercher, M.L. Marin,
[36] S. Zinatloo-Ajabshir, M.S. Morassaei, M. Salavati-Niasari, J. Colloid Interface M.A. Miranda, Catal. Today 129 (2007) 37e42.
Sci. 497 (2017) 298e308. [90] R.Y. Asahi, T.A. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293 (2001)
[37] F. Beshkar, S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mater. Sci. Mater. 269e271.
Electron. 26 (2015) 5043e5051. [91] D.M. Blake, Bibliography of Work on the Photocatalytic Removal of Haz-
[38] S. Zinatloo-Ajabshir, Z. Salehi, M. Salavati-Niasari, RSC Adv. 6 (2016) ardous Compounds from Water and Air, National Technical Information
107785e107792. Service, Springfield, 1999.
[39] A. Petala, A. Noe, Z. Frontistis, C. Drivas, S. Kennou, D. Mantzavinos, [92] U. Stafford, K.A. Gray, P.V. Kamat, Chem. Rev. 3 (1996) 77e104.
D.I. Kondarides, J. Hazard. Mater. (2018), https://doi.org/10.1016/ [93] X. Chen, S.S. Mao, Chem. Rev. 107 (2007) 2891e2959.
j.jhazmat.2018.03.008. [94] O. Legrini, E. Oliveros, A.M. Braun, Chem. Rev. 93 (1993) 671e698.
[40] S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mater. Sci. Mater. Electron. 26 [95] J. Zhao, X. Yang, Build. Environ. 38 (2003) 645e654.
(2015) 5812e5821. [96] N.T. Dung, N.V. Khoa, J.M. Herrmann, Inter. J. Photoenergy 7 (2005) 11e15.
[41] S. Zinatloo-Ajabshir, M. Salavati-Niasari, M. Hamadanian, J. Mater. Sci. Mater. [97] S. Sur, Z. Ozturk, M. Oztas, M. Bedir, Phys. Scr. 82 (2010) 045604.
Electron. 27 (2016) 998e1006. [98] S.V. Sharma, P. Chand, Acta Phys. Pol. A 81 (1992) 653e658.
[42] S. Zinatloo-Ajabshir, M. Salavati-Niasari, J. Mater. Sci. Mater. Electron. 27 [99] E.K. Goharshadi, R. Mehrkhah, P. Nancarrow, Mater. Sci. Semiconductor
(2016) 3918e3928. Process. 16 (2013) 356e362.
110 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
[100] J.S. Hu, L.L. Ren, Y.G. Guo, H.P. Liang, A.M. Cao, L.J. Wan, C.L. Bai, Angew Chem.
Int. Ed. 117 (2005) 1295e1299.
[101] Y. Qin, Z. Sun, W. Zhao, Z. Liu, D. Ni, Z. Ma, Nano-Struct. Nano-Objects 10
(2017) 176e181.
[102] J. Lee, S. Ham, D.J. Jang, J. Environ. Chem. Eng. 5 (2017) 4431e4440.
[103] H. Fujiwara, H. Hosokawa, K. Murakoshi, Y. Wada, S. Yanagida, Langmuir 14
(1998) 5154e5159.
[104] G.J. Lee, A. Manivel, V. Batalova, G. Mokrousov, S. Masten, J. Wu, Indust. Eng.
Chem. Res. 52 (2013) 11904e11912.
[105] R.A. Tigaa, G.J. Lucas, A. de Bettencourt-Dias, Inorg. Chem. 56 (2017)
3260e3268.
[106] Z. Chen, R. Wu, H. Wang, Y. Jiang, L. Jin, Y. Guo, Y. Song, F. Fang, D. Sun, Chem.
Eng. J. 326 (2017) 680e690.
[107] L.W. Yin, Y. Bando, J.H. Zhan, M.S. Li, D. Golberg, Adv. Mater. 17 (2005)
1972e1977.
[108] S. Ham, D.J. Jang, J. Environ. Chem. Eng. 6 (2018) 228e235.
[109] J. Liu, Z. Guo, Y. Jia, F. Meng, T. Luo, J. Liu, J. Cryst, Growth 311 (2009)
1423e1429.
[110] F.A. La Porta, A.E. Nogueira, Lourdes Gracia, W.S. Pereira, G. Botelho,
T.A. Mulinari, J. Andre
s, E. Longo, J. Phy. Chem. Solids 103 (2017) 179e189.
[111] F. Wei, X. Lu, Y. Wu, Z. Cai, L. Liu, P. Zhou, Q. Hu, Chem. Eng. J 226 (2013)
416e422.
[112] A. Tiwari, S. Khan, R. Kher, M. Mehta, S. Dhoble, J. Lumin. 131 (2011)
1172e1176.
[113] H.R. Pouretedal, A. Norozi, M.H. Keshavarz, A. Semnani, J. Hazard. Mater. 162
(2009) 674e681.
[114] C.V. Reddy, J. Shim, M. Cho, J. Phys. Chem. Solids 103 (2017) 209e217.
[115] R.G. Solanki, P. Rajaram, Nano-Struct. Nano-Objects 12 (2017) 157e165.
[116] D. Pathania, S. Sarita, B.S. Rathore, Chalcogenide Lett. 8 (2011) 396e404.
[117] J.A. Ho, Y.C. Lin, L.S. Wang, K.C. Hwang, P.T. Chou, Anal. Chem. 81 (2009)
1340e1346.
[118] M. Arif, Q. Li, J. Yao, T. Huang, Y. Hua, T. Liu, X. Liu, J. Environ. Chem. Eng. 6
(2017) 5358e5368.
[119] J. Chen, F. Zhang, Y.L. Zhao, Y.C. Guo, P. Gong, Z.Q. Li, H.S. Qian, Appl. Surf. Sci.
362 (2016) 126e131.
[120] R.S. Ganesh, S.K. Sharma, E. Durgadevi, M. Navaneethan, H.S. Binitha,
S. Ponnusamy, C. Muthamizhchelvan, Y. Hayakawa, D.Y. Kim, Superlattices
Microstruct. 104 (2017) 247e257.
[121] M. Luo, Y. Liu, J. Hu, J. Li, J. Liu, R.M. Richards, Appl. Catal. B Environ. 125
(2012) 180e188.
[122] M. Luo, Y. Liu, J. Hu, H. Liu, J. Li, ACS Appl. Mater. Interface 4 (2012)
1813e1821.
[123] X.L. Liu, Y. Yan, Z.L. Da, W.D. Shi, C.C. Ma, P. Lv, Y.F. Tang, G.X. Yao, Y.T. Wu,
P.W. Huo, Y.S. Yan, Chem. Eng. J. 241 (2014) 243e250.
[124] N.H. Patel, M.P. Deshpande, S.H. Chaki, Mater. Sci. Semiconductor Process. 31
(2015) 272e280.
[125] X. Dai, M.L. Xie, S.G. Meng, X.L. Fu, S.F. Chen, Appl. Catal. B Environ. 158
(2014) 382e390.
[126] F.Q. Zhou, J.C. Fan, Q.J. Xu, Y.L. Min, Appl. Catal. B Environ. 201 (2017) 77e83.
[127] X. Yan, K. Liu, W. Shi, Colloids Surf. A Physicochem. Eng. Aspects 520 (2017)
138e145.
[128] Z. Hosseinpour, S. Hosseinpour, Mater. Sci. Semiconductor Process. 72 (2017)
32e36.
[129] R. Blachnik, A. Müller, Thermochim. Acta 361 (2000) 31e52.
[130] L. Chen, W. Yu, Y. Li, Powder Technol. 191 (2009) 52e54.
[131] T. Sakamoto, H. Sunamura, H. Kawaura, T. Hasegawa, T. Nakayama, M. Aono,
Appl. Phys. Lett. 82 (2003) 3032e3034.
[132] J.S. Chung, H.J. Sohn, J. Power Sources 108 (2002) 226e231.
[133] A. Setkus, A. Galdikas, A. Mironas, I. Simkiene, I. Ancutiene, V. Janickis,
S. Kaciulis, G. Mattogno, G.M. Ingo, Thin Solid Films 391 (2001) 275e281.
[134] X.P. Shen, H. Zhao, H.Q. Shu, H. Zhou, A.H. Yuan, J. Phys. Chem. Solids 70
(2009) 422e427.
[135] S. He, G.S. Wang, C. Lu, X. Luo, B. Wen, L. Guo, M.S. Cao, Chem. Plus. Chem. 78
(2013) 250e258.
[136] M. Basu, A.K. Sinha, M. Pradhan, S. Sarkar, Y. Negishi, T. Pal, Environ. Sci.
Technol. 44 (2010) 6313e6318.
[137] W. Fu, M. Liu, F. Xue, X. Wang, Z. Diao, L. Guo, RSC Adv. 6 (2016)
80361e80367.
[138] M. Peng, L.L. Ma, Y.G. Zhang, M. Tan, J.B. Wang, Y. Yu, Mater. Res. Bull. 44
(2009) 1834e1841.
[139] U. Shamraiz, A. Badshah, R.A. Hussain, M.A. Nadeem, S. Saba, J. Saudi Chem.
Soc. 21 (2017) 390e398.
[140] W. Zhang, Y. Sun, X. Zhiyin, W. Li, B. Li, X. Huang, X. Liu, J. Hu, J. Mater. Chem.
A 3 (2015) 7304e7313.
[141] X.S. Hu, Y. Shen, Y.T. Zhang, J.J. Nie, J. Phys, Chem. Solids 103 (2017)
201e208.
[142] B. Zhao, S. Li, Q. Zhang, Y. Wang, C. Song, Z. Zhang, K. Yu, Chem. Eng. J. 230
(2013) 236e243.
[143] S.I. Sadovnikov, Y.V. Kuznetsova, A.A. Rempel, Nano-Struct. Nano-Objects 7
(2016) 81e91.
[144] Y. Zhang, J. Xia, C. Li, G. Zhou, W. Yang, D. Wang, H. Zheng, Y. Du, X. Li, Q. Li,
J. Mater. Sci. 52 (2017) 9424e9429.
[145] S.I. Sadovnikov, E.A. Kozlova, E.Y. Gerasimov, A.A. Rempel, Catal. Commun.
100 (2017) 178e182.
[146] K. Nagasuna, T. Akita, M. Fujishima, H. Tada, Langmuir 27 (2011) 7294e7300.
[147] J.J. Wu, R.C. Chang, D.W. Chen, C.T. Wu, Nanoscale 4 (2012) 1368e1372.
[148] R. Boughalmi, A. Boukhachem, I. Gaied, K. Boubaker, M. Bouhafs, M. Amlouk,
Mater. Sci. Semiconductor Process. 16 (2013) 1584e1591.
[149] A. Pourahmad, S. Sohrabnezhad, J. Alloys Compd. 484 (2009) 314e316.
[150] E.S. Aazam, J. Ind. Eng. Chem. 20 (2014) 4033e4038.
[151] H.H. Li, J. Yang, J.Y. Zhang, M. Zhou, RSC Adv. 2 (2012) 6258e6261.
[152] K. Mageshwari, R.H. Sathyamoorthy, Mater. Sci. Semiconductor Process. 16
(2013) 43e50.
[153] F. Chen, Y. Cao, D. Jia, J. Colloid Interface Sci. 404 (2013) 110e116.
[154] D. Ayodhya, G. Veerabhadram, Superlattices Microstruct. 102 (2017)
103e118.
[155] L. Cademartiri, F. Scotognella, P.G. Brien, B.V. Lotsch, J. Thomson, S. Petrov,
N.P. Kherani, G.A. Ozin, Nano Lett. 9 (2009) 1482e1486.
[156] A.A. Tahir, M.A. Ehsan, M. Mazhar, K.U. Wijayantha, M. Zeller, A.D. Hunter,
Chem. Mater. 22 (2010) 5084e5092.
[157] G. Konstantatos, L. Levina, J. Tang, E.H. Sargent, Nano Lett. 8 (2008)
4002e4006.
[158] I.M. Kobasa, G.P. Tarasenko, Theor. Exp. Chem. 38 (2002) 255e258.
[159] M. Lu, G. Yuan, Z. Wang, Y. Wang, J. Guo, Nanoscale Res. Lett. 10 (2015) 385.
[160] J. Cao, B. Xu, H. Lin, B. Luo, S. Chen, Catal. Commun. 26 (2012) 204e208.
[161] Z. Fang, Y. Liu, Y. Fan, Y. Ni, X. Wei, K. Tang, J. Shen, Y. Chen, J. Phys. Chem. C
115 (2011) 13968e13976.
[162] J. Wang, X. Zhang, J. Wu, H. Chen, S. Sun, J. Bao, S. Li, H. Bi, Nanoscale (2017),
https://doi.org/10.1039/C7NR04593J.
[163] L. Zhang, H.B. Wu, X.W. Lou, Chem. Commun. 48 (2012) 6912e6914.
[164] Y. Zhou, C. Wu, H. Zhang, X. Wu, Z. Fu, Electrochim. Acta 52 (2007)
3130e3136.
[165] Z.D. Meng, K. Ullah, L. Zhu, S. Ye, W.C. Oh, Mater. Sci. Semiconductor Process.
27 (2014) 173e180.
[166] Y. Kim, J.B. Goodenough, J. Phys. Chem. C 112 (2008) 15060e15064.
[167] H.Y. He, Appl. Surface Sci. (2016), https://doi.org/10.1016/
j.apsusc.2016.10.128.
[168] S. Sohrabnezhad, A. Pourahmad, E. Radaee, J. Hazard. Mater. 170 (2009)
184e190.
[169] G. Panthi, N.A. Barakat, K.A. Khalil, A. Yousef, K.S. Jeon, H.Y. Kim, Ceram. Int.
39 (2013) 1469e1476.
[170] M.S. Akhtar, A. Alenad, M.A. Malik, Mater. Sci. Semiconductor Process. 32
(2015) 1e5.
[171] S.K. Bhar, S. Jana, A. Mondal, N. Mukherjee, J. Colloid Interface Sci. 393 (2013)
286e290.
[172] M. Gong, Q. Liu, R. Goul, D. Ewing, M. Casper, A. Stramel, A. Elliot, J.Z. Wu, ACS
Appl. Mater. Interfaces 9 (2017) 27801e27808.
[173] F. Long, J. He, M. Zhang, X. Wu, S. Mo, Z. Zou, Y. Zhou, J. Mater. Sci. 50 (2015)
1848e1854.
[174] A.K. Dutta, S.K. Maji, D.N. Srivastava, A. Mondal, P. Biswas, P. Paul,
B. Adhikary, ACS Appl. Mater. Interfaces 4 (2012) 1919e1927.
[175] J.L. Machol, F.W. Wise, R.C. Patel, D.B. Tanner, Phys. Rev. B 48 (1993)
2819e2822.
[176] M. Brumer, A. Kigel, L. Amirav, A. Sashchiuk, O. Solomesch, N. Tessler,
E. Lifshitz, Adv. Funct. Mater. 15 (2005) 1111e1116.
[177] E. Sarica, V. Bilgin, Mater. Sci. Semiconductor Process. 68 (2017) 288e294.
[178] A. Santra, G. Mondal, M. Acharjya, P. Bera, A. Jana, S. Seok, P. Bera, Nano-
Struct. Nano-Objects 10 (2017) 91e99.
[179] R.F. Howe, Asia Pacific J. Chem. Eng. 6 (1998) 55e84.
[180] M.A. Zhukobskiy, A.L. Stryuk, V.V. Shvalagin, N.P. Smirnova, O.S. Lytvyn,
A.M. Eremenko, J. Photochem. Photobiol. A Chem. 203 (2009) 137e144.
[181] D. Kumar, R. Bai, S. Chaudhary, D.K. Pandya, Mater. Today Energy 6 (2017)
105e114.
[182] N.B. Rahna, V. Kalarivalappil, M. Nageri, S.C. Pillai, S.J. Hinder, V. Kumar,
B.K. Vijayan, Mater. Sci. Semiconductor Process. 42 (2016) 303e310.
[183] G.J. Zhou, M.K. Lu, Z.L. Xiu, S.F. Wang, H.P. Zhang, Y.Y. Zhou, S.M. Wang,
J. Phys. Chem. B 110 (2006) 6543e6548.
[184] R. Jin, G. Chen, Q. Wang, J. Pei, Mater. Lett. 65 (2011) 1151e1153.
[185] M. Kaur, C.M. Nagaraja, RSC Adv. 6 (2016) 56790e56799.
[186] W. Wu, Y. He, Y. Wu, T. Wu, J. Alloys Compd. 509 (2011) 9356e9362.
[187] E. Shah, J.V. Vaghasiya, S.S. Soni, C.J. Panchal, P.S. Suryavanshi, M. Chavda,
H.P. Soni, J. Environ. Chem. Eng. 4 (2016) 4708e4718.
[188] L. Shao, D. Jiang, P. Xiao, L. Zhu, S. Meng, M. Chen, Appl. Catal. B Environ. 198
(2016) 200e210.
[189] S. Ahluwalia, N.T. Prakash, R. Prakash, B. Pal, Chem. Eng. J. 306 (2016)
1041e1048.
[190] T. Mahvelati, E.K. Goharshadi, Ultrason. Sonochem. 34 (2017) 78e89.
[191] S. Allahveran, A. Mehrizad, J. Mol. Liq. 225 (2017) 339e346.
[192] M. Mehrabian, Z. Esteki, Optik Int. J. Light Electron Optics 130 (2017)
1168e1172.
[193] L. Kashinath, K. Namratha, K. Byrappa, J. Alloys Compd. 695 (2017) 799e809.
[194] S. Kaur, S. Sharma, A. Umar, S. Singh, S.K. Mehta, S.K. Kansal, Superlattices
Microstruct. 103 (2017) 365e375.
[195] P.S. Yoo, D.A. Reddy, Y. Jia, S.E. Bae, S. Huh, C. Liu, J. Colloid Interface Sci. 486
(2017) 136e143.
[196] A. Eyasu, O.P. Yadav, R.K. Bachheti, Int. J. Chem. Tech. Res. 5 (2013)
1452e1461.
[197] J. Lee, Y. Kim, J.K. Kim, S. Kim, D.H. Min, D.J. Jang, Appl. Catal. B Environ 205
(2017) 433e442.
[198] B. Kaur, K. Singh, A.K. Malik, Dyes Pigments 142 (2017) 153e160.
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
[199] H.R. Rajabi, H. Arjmand, H. Kazemdehdashti, M. Farsi, J. Environ. Chem. Eng.
4 (2016) 2830e2840.
[200] K. Kalpana, V. Selvaraj, J. Ind. Eng. Chem. 41 (2016) 105e113.
[201] S. Kaur, S. Sharma, S.K. Kansal, Superlattices Microstruct. 98 (2016) 86e95.
[202] D. Pathania, D. Gupta, H. Alaa, G. Sharma, A. Kumar, M. Naushad, T. Ahamad,
S.M. Alshehri, J. Photochem. Photobiol. A Chem. 329 (2016) 61e68.
[203] S. Thangavel, K. Krishnamoorthy, S.J. Kim, G. Venugopal, J. Alloys Compd. 683
(2016) 456e462.
[204] G. Naudin, T. Entradas, B. Barrocas, O.C. Monteiro, J. Mater. Sci. Tech. 32
(2016) 1122e1128.
[205] U. Jabeen, S.M. Shah, S.U. Khan, Surf. Interfaces 6 (2017) 40e49.
[206] J. Osuntokun, P.A. Ajibade, D.C. Onwudiwe, Superlattices Microstruct. 100
(2016) 605e618.
[207] L. Yin, D. Zhang, J. Ma, X. Kong, J. Huang, H. Zhang, C. Liu, Powder Technol.
301 (2016) 1085e1091.
[208] R. Khaparde, S. Acharya, Spectrochim. Acta Part A Mol. Biomol. Spectros. 163
(2016) 49e57.
[209] L. Yin, D. Wang, J. Huang, L. Cao, H. Ouyang, X. Yong, J. Alloys Compd. 664
(2016) 476e480.
[210] A. Dumbrava, D. Berger, G. Prodan, C. Matei, F. Moscalu, A. Diacon, Mater.
Chem. Phys. 193 (2017) 316e328.
[211] Y. Hanifehpour, B. Soltani, A.R. Amani-Ghadim, B. Hedayati, B. Khomami,
S.W. Joo, J. Ind. Eng. Chem. 34 (2016) 41e50.
[212] Q. Ma, Y. Wang, J. Kong, H. Jia, Ceramics Int. 42 (2016) 2854e2860.
[213] L. Hu, F. Chen, P. Hu, L. Zou, X. Hu, J. Mol. Catal. A Chem. 411 (2016) 203e213.
[214] Y. Tang, J. Tian, T. Malkoske, W. Le, B. Chen, J. Mater. Sci. 52 (2017)
1581e1589.
[215] F. Chen, Y. Cao, D. Jia, A. Liu, Dyes Pigments 120 (2015) 8e14.
[216] D. Samanta, T.I. Chanu, S. Chatterjee, Mater. Res. Bull. 88 (2017) 85e90.
[217] N. Dixit, J.V. Vaghasia, S.S. Soni, M. Sarkar, M. Chavda, N. Agrawal, H.P. Soni,
J. Environ. Chem. Eng. 3 (2015) 1691e1701.
[218] D. Ayodhya, M. Venkatesham, A.S. Kumari, K.G. Mangatayaru,
G. Veerabhadram, J. Appl. Chem. 6 (2013) 101e109.
[219] D. Ayodhya, G. Veerabhadram, J. Fluoresc. 26 (2016) 2165e2175.
[220] N. Priyadharsini, M. Elango, S. Vairam, M. Thamilselvan, Mater. Sci. Semi-
conductor Process. 49 (2016) 68e75.
[221] C. Wang, Y. Ao, P. Wang, S. Zhang, J. Qian, J. Hou, Appl. Surf. Sci. 256 (2010)
4125e4128.
[222] M. El-Kemary, H. El-Shamy, J. Photochem. Photobiol. A Chem. 205 (2009)
151e155.
[223] F. Chen, Y. Cao, D. Jia, Chem. Eng. J 234 (2013) 223e231.
[224] C. Mondal, A. Singh, R. Sahoo, A.K. Sasmal, Y. Negishi, T. Pal, New J. Chem. 39
(2015) 5628e5635.
[225] Y. Feng, N. Feng, G. Zhang, G. Du, Cryst. Eng. Comm. 16 (2014) 214e222.
[226] M. Kaur, N.K. Gupta, C.M. Nagaraja, Cryst. Eng. Comm. 17 (2015) 2359e2367.
[227] A.K. Kole, C.S. Tiwary, P. Kumbhakar, Cryst. Eng. Comm. 15 (2013)
5515e5525.
[228] W. Yang, X. Liu, D. Li, L. Fan, Y. Li, Phys. Chem. Chem. Phys. 17 (2015)
14532e14541.
[229] X. Wang, Y. Li, M. Wang, W. Li, M. Chen, Y. Zhao, New J. Chem. 38 (2014)
4182e4189.
[230] S. Ham, Y. Kim, M.J. Park, B.H. Hong, D.J. Jang, RSC Adv. 6 (2016)
24115e24120.
[231] S. Shuang, Z. Xie, Z. Zhang, J. Colloid Interface Sci. 494 (2017) 107e113.
[232] B. Ahmed, A.K. Ojha, S. Kumar, Spectrochim. Acta Part A Mol. Biomol.
Spectros. 179 (2017) 144e154.
[233] P. Zhou, Y. Xie, J. Fang, Y. Ling, C. Yu, X. Liu, Y. Dai, Y. Qin, D. Zhou, Che-
mosphere 178 (2017) 1e10.
[234] Q. Cai, Z. Hu, Q. Zhang, B. Li, Z. Shen, Appl. Surf. Sci. 403 (2017) 151e158.
[235] B. Wang, W. Feng, L. Zhang, Y. Zhang, X. Huang, Z. Fang, P. Liu, Appl. Catal. B
Environ. 206 (2017) 510e519.
[236] J. Lv, D. Li, K. Dai, C. Liang, D. Jiang, L. Lu, G. Zhu, Mater. Chem. Phys. 186
(2017) 372e381.
[237] S.G. Ghugal, R.R. Mahalik, P.S. Charde, S.S. Umare, S.B. Kokane, V. Sudarsan,
R. Sasikala, Micropor. Mesopor. Mater. 242 (2017) 284e293.
[238] L. Hu, G. Deng, W. Lu, S. Pang, X. Hu, Appl. Surf. Sci. 410 (2017) 401e413.
[239] A. Khan, R. Khan, A. Waseem, A. Iqbal, Z.H. Shah, Inorg. Chem. Commun. 72
(2016) 33e41.
[240] M. Sun, Y. Wang, Y. Fang, S. Sun, Z. Yu, J. Alloys Compd. 684 (2016) 335e341.
[241] M.E. Khan, M.M. Khan, M.H. Cho, J. Colloid Interface Sci. 482 (2016) 221e232.
[242] F. Tian, D. Hou, F. Hu, K. Xie, X. Qiao, D. Li, Appl. Surf. Sci. 391 (2017)
295e302.
[243] Q. Fan, Y. Huang, C. Zhang, J. Liu, L. Piao, Y. Yu, S. Zuo, B. Li, Catal. Today 264
(2016) 250e256.
[244] S. Li, D. Meng, L. Hou, D. Wang, T. Xie, Appl. Surf. Sci. 371 (2016) 164e171.
[245] X. Fu, Y. Zhang, P. Cao, H. Ma, P. Liu, L. He, J. Peng, J. Li, M. Zhai, Radiat. Phys.
Chem. 123 (2016) 79e86.
[246] X. Yang, Y. Wang, Z. Wang, X. Lv, H. Jia, J. Kong, M. Yu, Ceramics Int. 42 (2016)
7192e7202.
[247] J. Guo, M. Guo, D. Jia, X. Song, F. Tong, Chem. Phys. Lett. 659 (2016) 66e69.
[248] A. Samadi-Maybodi, M.R. Sadeghi-Maleki, Spectrochim. Acta Part A Mol.
Biomol. Spectros. 152 (2016) 156e164.
[249] S. Fang, S. Xue, C. Wang, G. Wang, X. Wang, Q. Liang, Z. Li, S. Xu, Ceramics Int.
42 (2016) 4421e4428.
111
[250] L. Zhang, F. Huang, C. Liang, L. Zhou, X. Zhang, Q. Pang, J. Taiwan Inst. Chem.
Eng. 60 (2016) 643e650.
[251] F. Chen, D. Jia, Y. Cao, X. Jin, A. Liu, Ceramics Int. 41 (2015) 14604e14609.
[252] Y. Liu, M. Chi, H. Dong, H. Jia, B. Xu, Z. Zhang, Appl. Surf. Sci. 313 (2014)
558e562.
[253] Q. Liu, J. Li, Y. Zhao, Y. Zhou, C. Li, Mater. Lett. 138 (2015) 89e91.
[254] X. Guo, C. Chen, W. Song, X. Wang, W. Di, W. Qin, J. Mol. Catal. A Chem. 387
(2014) 1e6.
[255] G. Sun, C. Zhu, J. Zheng, B. Jiang, H. Yin, H. Wang, S. Qiu, J. Yuan, M. Wu,
W. Wu, Q. Xue, Mater. Lett. 166 (2016) 113e115.
[256] N. Qutub, B.M. Pirzada, K. Umar, O. Mehraj, M. Muneer, S. Sabir, Physica E 74
(2015) 74e86.
[257] D. Peng, H. Wang, K. Yu, Y. Chang, X. Ma, S. Dong, RSC Adv. 6 (2016)
77760e77767.
[258] H. Kiziltaş, T. Tekіn, Chem. Eng. Commun. 204 (2017) 689e694.
[259] Q. Wang, S. Zhang, J. He, L. Wang, Y. Shi, W. Zhou, H. She, F. Wang, J. Mater.
Sci. Mater. Electron. 28 (2017) 10464e10471.
[260] P. Prasannalakshmi, N. Shanmugam, J. Solid State Electrochem. 21 (2017)
1751e1766.
[261] Y. Wang, X. Yang, T. Ye, C. Xu, F. Xia, D. Meng, J. Electron. Mater. 46 (2017)
1598e1606.
[262] P. Govindhan, C. Pragathiswaran, J. Mater. Sci. Mater. Electron. 28 (2017)
5063e5069.
[263] Y. Hanifehpour, B. Soltani, A.R. Amani-Ghadim, H. Hodayi, B.K. Min, S.W. Joo,
J. Inorg. Organometall. Polym. Mate. 27 (2017) 1e12.
[264] H. Wang, T. Jin, X. Zheng, B. Jiang, C. Zhu, X. Yuan, J. Zheng, M. Wu,
J. Nanopart. Res. 18 (2016) 339.
[265] C.V. Reddy, S.P. Vattikuti, J. Shim, J. Mater. Sci. Mater. Electron. 27 (2016)
7799e7808.
[266] S. Sharma, S. Singh, N. Khare, Colloid Polym. Sci. 294 (2016) 917e926.
[267] L. Wu, M. Zhang, J. Li, C. Cen, X. Li, Res. Chem. Intermed. 42 (2016)
4569e4580.
[268] J. Wen, C.J. Liu, Y. Du, C.Y. Hu, X.Y. Tian, J. Cent. South Univ. 22 (2015)
4551e4559.
[269] L. An, G. Wang, Y. Cheng, L. Zhao, F. Gao, Y. Cheng, Rus. J. Phys. Chem. A 89
(2015) 1878e1883.
[270] D. Ayodhya, M. Venkatesham, A.S. Kumari, G.B. Reddy, D. Ramakrishna,
G. Veerabhadram, J. Fluoresc. 25 (2015) 1481e1492.
[271] D. Ayodhya, M. Venkatesham, A.S. Kumari, G.B. Reddy, G. Veerabhadram, Int.
J. Ind. Chem. 6 (2015) 261e271.
[272] M.E. Hern
andez-Torres, M.T. Ojeda-Carrera, M. Sa
nchez-Cantú, N.R. Silva-
Gonza
lez, J.M. Gracia-Jime
nez, Chem. Papers 68 (2014) 1257e1264.
[273] G. Lin, J. Zheng, R. Xu, J. Phys. Chem. C 112 (2008) 7363e7370.
[274] C.V. Reddy, R.V. Ravikumar, G. Srinivas, J. Shim, M. Cho, Mater. Sci. Eng. B 221
(2017) 63e72.
[275] Q. Wang, Y. Shi, T. Niu, J. He, H. She, B. Su, J. Sol-Gel Sc. Technol. 83 (2017)
555e566.
[276] M. Shaban, M. Mustafa, A.M. El Sayed, Mater. Sci. Semiconductor Process. 56
(2016) 329e343.
[277] D. Ayodhya, G. Veerabhadram, Mater. Sci. Eng. B 225 (2017) 33e44.
[278] S. Li, Z. Zhang, L. Yan, S. Jiang, N. Zhu, J. Li, W. Li, S. Yu, J. Supercrit. Fluids 123
(2017) 11e17.
[279] K. Subramanyam, N. Sreelekha, D.A. Reddy, G. Murali, K.R. Varma,
R.P. Vijayalakshmi, Solid State Sci. 65 (2017) 68e78.
[280] N. Sreelekha, K. Subramanyam, D.A. Reddy, G. Murali, K.R. Varma,
R.P. Vijayalakshmi, Solid State Sci. 62 (2016) 71e81.
[281] M. Maleki, M. Haghighi, J. Mol. Catal. A Chem. 424 (2016) 283e296.
[282] S. Farhadi, F. Siadatnasab, Mater. Res. Bull. 83 (2016) 345e353.
[283] H.Y. He, Micropor. Mesopor. Mater. 227 (2016) 31e38.
[284] X. Chen, H. Li, Y. Wu, H. Wu, L. Wu, P. Tan, J. Pan, X. Xiong, J. Colloid Interface
Sci. 476 (2016) 132e143.
[285] S. Li, Z.H. Ge, B.P. Zhang, Y. Yao, H.C. Wang, J. Yang, Y. Li, C. Gao, Y.H. Lin, Appl.
Surface Sci. 384 (2016) 272e278.
[286] H. Mazaheri, M. Ghaedi, A. Asfaram, S. Hajati, J. Mol. Liq. 219 (2016)
667e676.
[287] Y.Y. Lu, Y.Y. Zhang, J. Zhang, Y. Shi, Z. Li, Z.C. Feng, C. Li, Appl. Surf. Sci. 370
(2016) 312e319.
[288] X.S. Hu, Y. Shen, L.H. Xu, L.M. Wang, Y.J. Xing, J. Alloys Compd. 674 (2016)
289e294.
[289] Q. Wang, Y. Shi, L. Pu, Y. Ta, J. He, S. Zhang, J. Zhong, J. Li, B. Su, Appl. Surface
Sci. 367 (2016) 109e117.
[290] C. Feng, X. Meng, X. Song, X. Feng, Y. Zhao, G. Liu, RSC Adv. 6 (2016)
110266e110273.
[291] Y.Q. Zhang, S. Li, B.P. Zhang, RSC Adv. 6 (2016) 103215e103223.
[292] Q. Li, F. Wang, L. Sun, Z. Jiang, T. Ye, M. Chen, Q. Bai, C. Wang, X. Han, Nano-
Micro Lett. 9 (2017) 35.
[293] Y. Cui, C. Wei, J. Yang, J. Zhang, W. Zheng, Cryst. Eng. Comm. 18 (2016)
6245e6253.
[294] A.C. Estrada, F.M. Silva, S.D. Soares, J.A.P. Coutinho, T. Trindade, RSC Adv. 6
(2016) 34521e34528.
[295] G. Hou, Z. Cheng, L. Kang, X. Xu, F. Zhang, H. Yang, Cryst. Eng. Comm. 17
(2015) 5496e5501.
[296] S. Harish, J. Archana, M. Navaneethan, S. Ponnusamy, A. Singh, V. Gupta,
D.K. Aswal, H. Ikeda, Y. Hayakawa, RSC Adv. 7 (2017) 34366e34375.
112 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
[297] Z. Hosseinpour, A. Alemi, A. Khandar, X. Zhao, Y. Xie, New J. Chem. 39 (2015)
5470e5476.
[298] X. Deng, C. Wang, H. Yang, M. Shao, S. Zhang, X. Wang, M. Ding, J. Huang,
X. Xu, Sci. Rep. 7 (2017) 3877.
[299] M. Saranya, R. Ramachandran, P. Kollu, S.K. Jeong, A.N. Grace, RSC Adv. 5
(2015) 15831e15840.
[300] M. Tanveer, C. Cao, I. Aslam, Z. Ali, F. Idrees, W.S. Khan, M. Tahir, S. Khalid,
G. Nabi, A. Mahmood, New J. Chem. 39 (2015) 1459e1468.
[301] M. Tanvir, C. Cao, I. Aslam, Z. Ali, F. Idrees, M. Tahir, W.S. Khan, F.K. Butt,
A. Mahmood, RSC Adv. 4 (2014) 63447e63456.
[302] Y.Q. Zhang, B.P. Zhang, L.F. Zhu, RSC Adv. 4 (2014) 59185e59193.
[303] G. Mondal, P. Bera, A.K. Santra, S. Jana, T.N. Mandal, A. Mondal, S. Seokc,
P. Bera, New J. Chem. 38 (2014) 4774e4782.
[304] L. Song, Y. Zeng, Y. Cheng, G. Luo, Mater. Res. Innov. 21 (2017) 232e236.
[305] M. Tanveer, C. Cao, Z. Ali, I. Aslam, F. Idrees, W.S. Khan, F.K. But, M. Tahir,
N. Mahmood, Cryst. Eng. Comm. 16 (2014) 5290e5300.
[306] X.H. Guan, P. Qu, X. Guan, G.S. Wang, RSC Adv. 4 (2014) 15579e15585.
[307] D. Ayodhya, M. Venkatesham, A.S. Kumari, G.B. Reddy, D. Ramakrishna,
G. Veerabhadram, J. Exp. Nanosci. 11 (2016) 418e432.
[308] J. Kundu, D. Pradhan, ACS Appl. Mater. Interface 6 (2014) 1823e1834.
[309] L. Gao, J. Du, T. Ma, Ceramics Int. 43 (2017) 9559e9563.
[310] F. Li, J. Wu, Q. Qin, Z. Li, X. Huang, Powder Technol. 198 (2010) 267e274.
[311] A. Malathi, J. Madhavan, J. Nano Res. 48 (2017) 49e61.
[312] T.Y. Ding, M.S. Wang, S.P. Guo, G.C. Guo, J.S. Huang, Mater. Lett. 62 (2008)
4529e4531.
[313] D. Ayodhya, G. Veerabhadarm, J. Inorg. Organomet. Polym. 27 (2017) 215e230.
[314] J. Tian, T. Yan, Z. Qiao, L. Wang, W. Li, J. You, B. Huang, Appl. Catal. B Environ.
209 (2017) 566e578.
[315] X. Hu, Y. Li, J. Tian, H. Yang, H. Cui, J. Ind. Eng. Chem. 45 (2017) 189e196.
[316] X.P. Qiu, J.S. Yu, H.M. Xu, W.X. Chen, W. Hu, H.Y. Bai, G.L. Chen, Appl. Surf. Sci.
362 (2016) 498e505.
[317] X. Zhang, X. Liu, L. Zhang, D. Li, S. Liu, J. Alloys Compd. 655 (2016) 38e43.
[318] W.L. Ong, G.W. Ho, Procedia Eng. 141 (2016) 7e14.
[319] X. Cheng, Q. Cheng, X. Deng, P. Wang, H. Liu, Electrochim. Acta 184 (2015)
264e275.
[320] S.K. Yadav, P. Jeevanandam, J. Alloys Compd. 649 (2015) 483e490.
[321] A. Sadollahkhani, I. Kazeminezhad, O. Nur, M. Willander, Mater. Chem. Phys.
163 (2015) 485e495.
[322] D.A. Reddy, R. Ma, M.Y. Choi, T.K. Kim, Appl. Surface Sci. 324 (2015)
725e735.
[323] D. Zhao, J. Fu, Y. Liu, F. Guo, A. Li, Funct. Mater. Lett. 10 (2017) 1750005.
[324] Z.D. Meng, L. Zhu, K. Ullah, S. Ye, Q. Sun, W.C. Oh, Chin. J. Catal. 34 (2013)
1527e1533.
[325] B. Subash, B. Krishnakumar, M. Swaminathan, M. Shanthi, Powder Technol.
241 (2013) 49e59.
[326] H. Zhang, B. Wei, L. Zhu, J. Yu, W. Sun, L. Xu, Appl. Surface Sci. 270 (2013)
133e138.
[327] A. Pourahmad, Superlattices Microstruct. 52 (2012) 276e287.
[328] Z. Lei, M. Zeda, T. Ghosh, O.W. Chun, Chin. J. Catal. 33 (2012) 254e260.
[329] G.M. Neelgund, A. Oki, Appl. Catal. B Environ. 110 (2011) 99e107.
[330] P. Ma, H. Yu, Y. Yu, W. Wang, H. Wang, J. Zhang, Z. Fu, Phys. Chem. Chem.
Phys. 18 (2016) 3638e3643.
[331] K. Kalpana, V. Selvaraj, RSC Adv. 6 (2016) 4227e4236.
[332] W.L. Ong, Y.F. Lim, J.L. Ong, G.W. Ho, J. Mater. Chem. A 3 (2015) 6509e6516.
[333] Q. Cao, R. Che, N. Chen, Chem. Commun. 50 (2014) 4931e4933.
[334] C. Xing, Y. Zhang, Z. Wu, D. Jiang, M. Chen, Dalton Trans. 43 (2014)
2772e2780.
[335] Z.D. Meng, T. Ghosh, L. Zhu, J.G. Choi, C.Y. Park, W.C. Oh, J. Mater. Chem. 22
(2012) 16127e16135.
[336] Y. Wang, M. Sun, Y. Fang, S. Sun, J. He, J. Mater. Sci. 51 (2016) 779e787.
[337] G. Murugadoss, R. Jayavel, M.R. Kumar, R. Thangamuthu, Appl. Nanosci. 6
(2016) 503e510.
[338] M. Ebadi, Z. Zarghami, M. Aliabadi, J. Mater. Sci. Mater. Electron. 27 (2016)
1622e1628.
[339] B. Zeng, W. Zeng, Nano 12 (2017) 1750005.
[340] W. Hu, L. Zhao, Y. Zhang, X. Zhang, L. Dong, S. Wang, Y. He, J. Exp. Nanosci. 11
(2016) 433e444.
[341] C. Yu, L. Wei, W. Zhou, D.D. Dionysiou, L. Zhu, Q. Shu, H. Liu, Chemosphere
157 (2016) 250e261.
[342] Z. Li, S. Xiong, G. Wang, Z. Xie, Z. Zhang, Sci. Rep. 6 (2016) 19754.
[343] B. Subash, B. Krishnakumar, M. Swaminathan, M. Shanthi, Spectrochim. Acta
Part A Mol. Biomol. Spectrosc. 105 (2013) 314e319.
[344] S. Kumar, A.P. Singh, C. Bera, M. Thirumal, B.R. Mehta, A.K. Ganguli, Chem.
Sus. Chem. 9 (2016) 1850e1858.
[345] Q. Zhao, S. Chen, L. Zhang, H. Huang, F. Liu, X. Liu, J. Nanopart. Res. 16 (2014)
2793.
[346] R. Tang, H. Su, Y. Sun, X. Zhang, L. Li, C. Liu, B. Wang, S. Zeng, D. Sun,
Nanoscale Res. Lett. 11 (2016) 126.
[347] W. Yang, L. Zhang, Y. Hu, Y. Zhong, H.B. Wu, X.W. Lou, Angew. Chem. Int. Ed.
51 (2012) 11501e11504.
[348] H. Jia, W. He, W.G. Wamer, X. Han, B. Zhang, S. Zhang, Z. Zheng, Y. Xiang,
J.J. Yin, J. Phys. Chem. C 118 (2014) 21447e21456.
[349] K. Kalpana, V. Selvaraj, Res. Chem. Intermed. 43 (2017) 423e435.
[350] D. Ayodhya, G. Veerabhadram, J. Photochem. Photobiol. B: Biol. 157 (2016)
57e69.
[351] H. Zhu, R. Jiang, J. Li, Y. Fu, S. Jiang, J. Yao, Sep. Purif. Technol. 179 (2017)
184e193.
[352] Y. Pei, X. Li, H. Chu, Y. Ge, P. Dong, R. Baines, L. Pei, M. Ye, J. Shen, Talanta 165
(2017) 44e51.
[353] Y. Liu, Y. Shi, X. Liu, H. Li, Appl. Surface Sci. 396 (2017) 58e66.
[354] K. Liang, C. Wang, X. Xu, J. Leng, H. Ma, Phys. Lett. A 381 (2017) 652e657.
[355] G. Zhao, D. Zhang, J. Yu, Y. Xie, W. Hu, F. Jiao, Ceramics Int. 43 (2017)
1580e15088.
[356] J. Rong, T. Zhang, F. Qiu, X. Rong, X. Zhu, X. Zhang, J. Alloys Compd. 685
(2016) 812e819.
[357] S. Boumaza, B. Bellal, A. Boudjemaa, M. Trari, Solar Energy 139 (2016)
444e451.
[358] A. Helal, F.A. Harraz, A.A. Ismail, T.M. Sami, I.A. Ibrahim, Mater. Design 102
(2016) 202e212.
[359] X. Gao, G. Huang, H. Gao, C. Pan, H. Wang, J. Yan, Y. Liu, H. Qiu, N. Ma, J. Gao,
J. Alloys Compd. 674 (2016) 98e108.
[360] S. Mosleh, M.R. Rahimi, M. Ghaedi, K. Dashtian, Ultrason. Sonochem. 32
(2016) 387e397.
[361] Y. Huang, W. Fan, B. Long, H. Li, F. Zhao, Z. Liu, Y. Tong, H. Ji, Appl. Catal. B
Environ. 185 (2016) 68e76.
[362] X. Li, Y. Li, J. Shenn, M. Ye, Ceramics Int. 42 (2016) 3154e3162.
[363] D.N. Xiong, G.F. Huang, B.X. Zhou, Q. Yan, A.L. Pan, W.Q. Huang, J. Colloid
Interface Sci. 464 (2016) 103e109.
[364] T.J. Entradas, J.F. Cabrita, B. Barrocas, M.R. Nunes, A.J. Silvestre, O.C. Monteiro,
Mater. Res. Bull. 72 (2015) 20e28.
[365] Y. Yan, Z. Zhou, X. Zhao, J. Zhou, J. Colloid Interface Sci. 435 (2014) 91e98.
[366] F. Liu, X. Shao, S. Yang, Mater. Sci. Semiconductor Process. 34 (2015)
104e108.
[367] S. Vadivel, A.N. Naveen, V.P. Kamalakannan, P. Cao, N. Balasubramanian,
Appl. Surface Sci. 351 (2015) 635e645.
[368] A. Sarkar, A.B. Ghosh, N. Saha, D.N. Srivastava, P. Paul, B. Adhikary, J. Colloid
Interface Sci. 483 (2016) 49e59.
[369] Y. Luo, H. Chen, X. Li, Z. Gong, X. Wang, X. Peng, M. He, Z. Sheng, Mater. Lett.
105 (2013) 12e15.
[370] S.V.P. Vattikuti, C. Byon, Superlattices Microstruct. 100 (2016) 514e525.
[371] N. Liang, J. Zai, M. Xu, Q. Zhu, X. Wei, X. Qian, J. Mater. Chem. A 2 (2014)
4208e4216.
[372] S. Balachandran, M. Swaminathan, Dalton Trans. 42 (2013) 5338e5347.
[373] Z. Wu, L. Chen, C. Xing, D. Jiang, J. Xie, M. Chen, Dalton Trans. 42 (2013)
12980e12988.
[374] D.K. Ma, M.L. Guan, S.S. Liu, Y.Q. Zhang, C.W. Zhang, Y.X. He, S.M. Huang,
Dalton Trans. 41 (2012) 5581e5586.
[375] J. Cao, B. Xu, H. Lin, B. Luo, S. Chen, Dalton Trans. 41 (2012) 11482e11490.
[376] G. Manna, R. Bose, N. Pradhan, Angew. Chem. Int. Ed. 53 (2014) 6743e6746.
[377] H.Y. He, Particulate Sci. Technol. 35 (2017) 410e417.
[378] T. Wu, X. Zhou, H. Zhang, X. Zhong, Nano Res. 3 (2010) 379e386.
[379] P. Lv, W. Fu, H. Yang, H. Sun, Y. Chen, J. Ma, X. Zhou, L. Tian, W. Zhang, M. Li,
H. Yao, Cryst. Eng. Comm. 15 (2013) 7548e7555.
[380] S. Luo, F. Chai, L. Zhang, C. Wang, L. Li, X. Liu, Z. Su, J. Mater. Chem. 22 (2012)
4832e4836.
[381] L.L. Long, J.J. Chen, X. Zhang, A.Y. Zhang, Y.X. Huang, Q. Rong, H.Q. Yu, NPG
Asia Mater. 8 (2016) e263.
[382] Z.Q. Liu, W.Y. Huang, Y.M. Zhang, Y.X. Tong, Cryst. Eng. Comm. 14 (2012)
8261e8267.
[383] L. Ren, D. Zhang, X.Y. Hao, X. Xiao, J.Y. Gong, M.Y. Wang, Z. Tong, Funct.
Mater. Lett. 10 (2017) 1750004.
[384] H.P. Jiao, X. Yu, Z.Q. Liu, P.Y. Kuang, Y.M. Zhang, RSC Adv. 5 (2015)
16239e16249.
[385] Y. Zhu, D. Xu, M. Meng, J. Mater. Sci. 50 (2015) 1594e1604.
[386] J. Lu, Z. Wang, Y. Zhang, X. Zhou, J. Nanomater. 2013 (2013) 29.
[387] J. Wang, J. Jin, X. Wang, S. Yang, Y. Zhao, Y. Wu, S. Dong, J. Sun, J. Sun,
J. Colloid Interface Sci. 505 (2017) 805e815.
[388] L. Chen, J. He, Q. Yuan, Y.W. Zhang, F. Wang, C.T. Au, S.F. Yin, RSC Adv. 5
(2015) 33747e33754.
[389] G. Gurumoorthy, P.J. Rani, S. Thirumaran, S. Ciattini, Inorgan. Chim. Acta 455
(2017) 132e139.
[390] M. Xu, H. Niu, J. Huang, J. Song, C. Mao, S. Zhang, C. Zhu, C. Chen, Appl. Surf.
Sc. 351 (2015) 374e381.
[391] S. Sohrabnezhad, Spectrosc. Acta Part A Mol. Biomol. Spectrosc. 81 (2011)
228e235.
[392] S. Lu, S. Ma, H. Wang, M. Shao, RSC Adv. 6 (2016) 78852e78857.
[393] Q. Xu, D. Jiang, T. Wang, S. Meng, M. Chen, RSC Adv. 6 (2016) 55039e55045.
[394] A. Pourahmad, S. Sohrabnezhad, E. Radaee, J. Porous Mater. 17 (2010)
367e375.
[395] S. Kong, Z. Jin, H. Liu, Y. Wang, J. Phys. Chem. C 118 (2014) 25355e25364.
[396] N. Rajawat, S. Benjamin, P.B. Punjabi, S.C. Ameta, Int. J. Chem. Sci. 7 (2009)
2313e2322.
[397] H.Y. He, Appl. Surf. Sci. 421 (2017) 260e267.
[398] Z. Wu, X. Yuan, H. Wang, Z. Wu, L. Jiang, H. Wang, L. Zhang, Z. Xiao, X. Chen,
G. Zeng, Appl. Catal. B Environ. 202 (2017) 104e111.
[399] V.G. Morales-Gallardo, A.M. Ayala, M. Pal, M.C. Jacome, J.T. Antonio,
N.R. Mathews, Chem. Phys. Lett. 660 (2016) 93e98.
[400] A. Kirkeminde, S. Ren, J. Mater. Chem. A 1 (2013) 49e54.
[401] A. Tian, Q. Xu, X. Shi, H. Yang, X. Xue, J. You, X. Wang, C. Dong, X. Yan,
H. Zhou, RSC Adv. 5 (2015) 62724e62731.
 D. Ayodhya, G. Veerabhadram / Materials Today Energy 9 (2018) 83e113
[402] G. Kaur, B. Singh, P. Singh, M. Kaur, K. Singh, K. Kaur, A. Thakur, R. Bala,
M. Kumar, A. Kumar, RSC Adv. 6 (2016) 99120e99128.
[403] X. Guo, Y. Fu, D. Hong, B. Yu, H. He, Q. Wang, L. Xing, X. Xue, Nanotechnology
27 (2016) 375704.
[404] G. Kaur, B. Singh, P. Singh, K. Singh, A. Thakur, M. Kumar, R. Bala, A. Kumar,
Chem. Select 2 (2017) 2166e2173.
[405] H. Sun, P.S. Tang, Adv. Mater. Res. 486 (2012) 55e59.
[406] B. Show, N. Mukherjee, A. Mondal, New J. Chem. 41 (2017) 10083e10095.
[407] S.K. Maji, A.K. Dutta, P. Biswas, D.N. Srivastava, P. Paul, A. Mondal,
B. Adhikary, Appl. Catal. A Gen. 419 (2012) 170e177.
[408] S. Liu, M. Li, S. Li, H. Li, L. Yan, Appl. Surf. Sci. 268 (2013) 213e217.
[409] X. Qu, Y. Hou, C. Wang, F. Du, L. Cao, RSC Adv. 5 (2015) 5307e5311.
[410] A. Kar, S. Sain, D. Rossouw, B.R. Knappett, S.K. Pradhan, A.E.H. Wheatley,
Nanoscale 8 (2016) 2727e2739.
[411] Q. Kang, S. Liu, L. Yang, Q. Cai, C.A. Grimes, ACS Appl. Mater. Interfaces 3
(2011) 746e749.
[412] Q. Li, T. Kako, J. Ye, J. Mater. Chem. 20 (2010) 10187e10192.
[413] C. Ratanatawanate, Y. Tao, K.J. Balkus, J. Phys. Chem. C 113 (2009)
10755e10760.
[414] H.Y. Wei, Y.P. Bai, H.Y. Zhang, Z.X. Liu, T.T. Li, H.S. Niu, L. Li, W.M. Zhang,
X.W. Li, Adv. Mater. Res. 1089 (2015) 129e132.
[415] V.R. Raja, D.R. Rosaline, A. Suganthi, M. Rajarajan, Solid State Sci. 67 (2017)
99e108.
[416] M.A. Zhengfa, X.W. Fengmei, W. Yijun, New Chem. Mater. 10 (2011) 036.
[417] M. Aliabadi, J. Mater, Sci. Mater. Electron. 26 (2015) 8892e8898.
[418] K. Hedayati, M. Kord, M. Goodarzi, D. Ghanbari, S. Gharigh, J. Mater. Sci.
Mater. Electron. 28 (2017) 1577e1589.
[419] W. Cui, M. Shao, L. Liu, Y. Liang, D. Rana, Appl. Surf. Sci. 276 (2013) 823e831.
[420] K. Ullah, Z.D. Meng, S. Ye, L. Zhu, W.C. Oh, J. Ind. Eng. Chem. 20 (2014)
1035e1042.
[421] S. Sehati, M.H. Entezari, Sep. Purif. Technol. 174 (2017) 482e492.
[422] C. Liu, Z. Liu, Y. Li, Z. Liu, Y. Wang, E. Lei, J. Ya, N. Gargiulo, D. Caputo, Mater.
Sci. Eng. B 177 (2012) 570e574.
[423] M. Zhang, Y. Xu, Z. Gong, J. Tao, Z. Sun, J. Lv, X. Chen, X. Jiang, G. He, P. Wang,
F. Meng, J. Alloys Compd. 649 (2015) 190e195.
[424] W. Cui, W. An, L. Liu, J. Hu, Y. Liang, Mater. Lett. 132 (2014) 251e254.
[425] L. Yang, X. Guan, G.S. Wang, X.H. Guan, B. Jia, New J. Chem. 41 (2017)
5732e5744.
[426] M. Lu, X. Wang, W. Cao, J. Yuan, M. Cao, Nanotechnology 27 (2016) 065702.
[427] N. Li, X. Zhang, S. Chen, X. Hou, J. Phys. Chem. Solids 72 (2011) 1195e1198.
[428] P.V. Quintana-Ramirez, M.C. Arenas-Arrocena, J. Santos-Cruz, M. Vega-
Gonza
lez, O. Martínez-Alvarez, V.M. Castan ~ o-Meneses, L.S. Acosta-Torres,
J. de la Fuente-Herna
ndez, Beilstein J. Nanotechnol. 5 (2014) 1542.
113
[429] L. Tan, S. Liu, Q. Yang, Y. Shen, Langmuir 31 (2015) 3958e3964.
[430] X. Zhou, X. Zhao, D. Zhang, S. Chen, X. Guo, W. Ding, Y. Chen, Nanotech-
nology 17 (2006) 3806.
[431] Y. Gu, Y. Xu, Y. Wang, ACS Appl. Mater. Interfaces 5 (2013) 801e806.
[432] W. Dong, X. Wang, B. Li, L. Wang, B. Chen, C. Li, X. Li, T. Zhang, Z. Shi, Dalton
Trans. 40 (2011) 243e248.
Dr. Dasari Ayodhya received his M.Sc. (Physical Chemistry)
degree from Osmania University, Hyderabad, India, in 2008
and Ph.D. degree in the field of Material Science from the
same university in 2016. To date, he has published more
than 22 research papers in reputed international journals.
His current research interest comprises of green synthesis
of semiconductor metal sulfide and metal oxide nano-
structures using various capping agents such as plant ma-
terials (leaf extracts, gums and latex), amino acids,
nucleosides, polymers, graphene-based materials and their
applications towards drug delivery, heavy metal ions detec-
tion, photocatalytic degradation of organic pollutants (dyes,
pesticides, nitrophenols, and industrial waste) and biolog-
ical activities (antimicrobial, antiviral and anticancer).
Dr. Veerabhadram Guttena is a Senior Professor in the
Department of Chemistry, Osmania University, Hyderabad,
India. He was also Former Head and Former Chairperson,
Board of Studies of the same Department. He received his
M.Sc. (1978) and Ph.D. (1982) in Chemistry from Osmania
University. He joined as an Assistant Professor in 1983 in
Department of Chemistry, Osmania University and in 1995
he was promoted as an Associate Professor in the same
University. Later he was promoted as a Professor of
Chemistry in 2003. He was a visiting professor at Omar
Mukhtar University, Libya (2009e2010). To date, he has
published more than 74 research papers in international
and national journals of repute and 10 students obtained
their Ph.D degrees under his supervision. His research
interests cover Electrochemistry, Green synthesis of metal, metal oxide and metal
sulfide nanostructures using plant extracts, gums, polymers; novel visible-light active
semiconductor nanocomposites, carbon nanomaterials and their applications towards
the sensors, catalysis, bio-imaging, drug delivery systems and photocatalytic degrada-
tion of organic pollutants for safety of the environment.