Journal of Hazardous Materials 415 (2021) 125588

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Journal of Hazardous Materials

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

Metal chalcogenide-based core/shell photocatalysts for solar hydrogen

production: Recent advances, properties and technology challenges
Vempuluru Navakoteswara Rao a, Parnapalle Ravi b, c, Marappan Sathish b, c,
Manavalan Vijayakumar d, Mohan Sakar e, Mani Karthik f, Subramanian Balakumar g,
Kakarla Raghava Reddy h, Nagaraj P. Shetti i, Tejraj M. Aminabhavi j, *, Muthukonda
Venkatakrishnan Shankar a
a
Nanocatalysis and Solar Fuels Research Laboratory, Department of Materials Science & Nanotechnology, Yogi Vemana University, Kadapa 516005, Andhra Pradesh,
India
b
Electrochemical Power Sources Division, Central Electrochemical Research Institute (CSIR-CECRI), Karaikudi 630003, Tamil Nadu, India
c
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad 201002, India
d
Global Innovative Centre for Advanced (GICAN), Nanomaterials, Collage of Science, Engineering and Environment, The University of Newcastle, Callaghan, NSW
2308, Australia
e
Centre for Nano and Material Sciences, Jain University, Bangalore 562112, Karnataka, India
f
Centre for Nanomaterials, International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Balapur, Hyderabad 500005, India
g
National Centre for Nanoscience and Nanotechnology, University of Madras, Guindy Campus, Chennai 600025, Tamil Nadu, India
h
School of Chemical and Biomolecular Engineering, The University of Sydney, Sydney, NSW 2006, Australia
i
Department of Chemistry, K. L. E. Institute of Technology, Gokul, Hubballi 580027, Karnataka, India
j
Department of Pharmaceutics, SETs’ College of Pharmacy, Dharwad 580007, Karnataka, India

A R T I C L E I N F O A B S T R A C T

Editor: Dr. Rinklebe Jörg Metal chalcogenides play a vital role in the conversion of solar energy into hydrogen fuel. Hydrogen fuel
technology can possibly tackle the future energy crises by replacing carbon fuels such as petroleum, diesel and
Keywords: kerosene, owning to zero emission carbon-free gas and eco-friendliness. Metal chalcogenides are classified into
Core-shell nanostructures narrow band gap (CdS, Cu2S, Bi2S3, MoS2, CdSe and MoSe2) materials and wide band gap materials (ZnS, ZnSe
Quantum dots
and ZnTe). Composites of these materials are fabricated with different architectures in which core-shell is one of
Metal-chalcogenides
the unique composites that drastically improve the photo-excitons separation, where chalcogenides in the core
Photocatalysts
Band gap can be well protected for sustainable uses. Thus,the core-shell structures promote the design and fabrication of
Stability composites with the required characteristics. Interestingly, the metal chalcogenides as a core-shell photocatalyst
S-Scheme heterojunction can be classified into type-I, reverse type-I, type-II and S-type nanocomposites, which can effectively influence
and significantly enhance the rate of hydrogen production. In this direction, this review is undertaken to provide
a comprehensive overview of the advanced preparation processes, properties of metal chalcogenides, and in
particular, photocatalytic performance of the metal chalcogenides as a core-shell photocatalysts for solar
hydrogen production.

1. Introduction 2019). Furthermore, hydrogen (H2) is used as a transportable chemical

The current rate of global energy consumption demands the best
alternative energy sources, especially from the sustainable and renew­
able energy processes, which should be environmentally benign pro­
cesses to produce zero carbon emission compared to fossil fuels (Qiu
et al., 2016; Grigioni et al., 2016; Rao et al., 2019; Li et al., 2018; Kudo
and Miseki, 2009; Abdalla et al., 2018; Wang et al., 2013; Han et al.,
fuel in many domestic applications, automobile sectors, industrial and
rocket fuel (Fig. 1) (Hisatomi et al., 2014; Colmenares and Luque, 2014;
Kuang et al., 2020; Vanneste et al., 2017; Safari and Dincer, 2020). Over
the past few decades, the generation of H2 via water splitting using
photocatalysts has gained much attention, which can be the best alter­
native fuel to replace carbon-based oils like diesel, kerosene, and petrol
(Sukumaran et al., 2011; Len and Luque, 2014; Xiao and Varma, 2016;

* Corresponding author.
E-mail address: aminabhavit@gmail.com (T.M. Aminabhavi).

https://doi.org/10.1016/j.jhazmat.2021.125588
Received 20 December 2020; Received in revised form 25 February 2021; Accepted 2 March 2021
Available online 11 March 2021
0304-3894/© 2021 Elsevier B.V. All rights reserved.
V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 1. Various industrial processes for H2 production and its multi-functional applications.

improved photocatalytic properties having large scale applications

(Hafeez et al., 2018; Bagheri et al., 2015; Li et al., 2016b, 2013b, 2019,
2015, 2017; Kavil et al., 2018; Zhu et al., 2016; Subha et al., 2018; Chen
et al., 2017a; Vamvasakis et al., 2016; David et al., 2018; Preethi and
Kanmani, 2013; Zhang et al., 2012; Yang et al., 2013c, 2017; Tian et al.,
2018; Zubair et al., 2020; Dong et al., 2019).
In addition to metal oxides, other noble metals, metal oxy-nitrides,
and carbonaceous materials have also been used as non-core/shell or
nanocomposites for photocatalytic applications (Chaudhuri and Paria,
2012; Parlett et al., 2013; Maeda et al., 2007, 2010; Sun et al., 2017b,
2017a; Yang et al., 2013a, 2014, 2013d; She et al., 2017; Wang et al.,
2014b, 2019; Xiong et al., 2013; Zhang et al., 2011, 2016; Ravi et al.,
2018; Liu et al., 2012; Shen et al., 2019). However, researchers are yet
facing many challenges such as exciton charge carrier recombination
(surface and bulk), photocorrosion, limited/poor visible/sunlight ac­
tivity, and inadequate band edge potentials. These drawbacks can be
overcome via the development of core-shell structured photocatalysts,
as these can exhibit controlled photocorrosion properties. Especially,
metal chalcogenides can control the excitons recombination and
enhance the reusability and recyclable stability for long hours usages
during the photocatalytic processes (Li et al., 2013c; Sang et al., 2011;
Rakkesh and Balakumar, 2013).

1.1. Literature review of metal chalcogenides-based photocatalysts and

Fig. 2. Various metal sulfides and their morphologies for energy production their applications in H2 production
and storage applications.
(Reprinted with permission, Copyright 2015, Royal Society Chemistry)
Researchers have developed metal chalcogenides for energy pro­
(Liu, 2016).
duction and storage applications (Fig. 2). Metal sulfides have unique
properties such as vacant d orbital and more sensitivity (Chen et al.,
Liu et al., 2018; Colón, 2016; Yuan et al., 2016). Over the years, research
2013; Tang et al., 2017). Zhang et al. (2013) examined CdS/g-C3N4
efforts have been expanded towards designing novel photocatalysts by
hierarchal nanostructures that have shown significant photocatalytic
varying different parameters in order to boost the photocatalytic H2
performances under visible light irradiation. Yang et al., developed
efficiency using homo and heterogeneous, ternary and binary nano­
CdS/ZnO core/shell nanofibers, which showed an excellent photo­
composites (Babu et al., 2015; Hafeez et al., 2018; Lakshmana Reddy
catalytic H2 evolution for longer hours (Yang et al., 2013b). Recently,
et al., 2017, 2018a; Liu et al., 2019; Praveen Kumar et al., 2015, 2016;
our research group studied the various types of metal chalcogenides
Rao et al., 2020a; Reddy et al., 2017a; Reddy et al., 2018a,b,c, 2021;
(CdS, Cu2S and CdSe) as the core and TiO2 or NiO as the shell materials
Kumari et al., 2018, 2017; Police et al., 2014; Urupalli et al., 2020;
for intensified photocatalytic H2 generation under sunlight, UV–visible,
Raghavan et al., 2020; Sharma et al., 2020; Kumar et al., 2019; Yusuf
and visible light irradiation (Rao et al., 2018, 2020b; Reddy et al.,
et al., 2019; Raghava et al., 2020; Manchala et al., 2019). Among these,
2018b; Lakshmana Reddy et al., 2018a; Navakoteswara Rao et al.,
the core-shell structured photocatalysts play the key roles to achieve the
2019). The list of chalcogenides-based photocatalyst for H2 production

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V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Table 1
Comparison of photocatalytic performance of metal chalcogenides-based photocatalysts for the efficient hydrogen production reported in the recent literature.
Photocatalyst Light source Amount of catalyst Reactant solution Rate of H2 production (µmol//h/ Ref.
(mg) gcat)

CdS/TiO2 UV–visible 5 0.3 M Na2SO4 & 0.3 M Na2S 2,58,526 (Rao et al., 2018)
CdS/ZnO Visible 50 0.1 M Na2SO4 & 0.04 M 354 (Yang et al., 2013b)
Na2SO3
ZnO/ZnS-PdS UV & 60 5% Glycerol 2141 (Liu et al., 2013b)
UV–Visible
CdS@TaON UV–Visible 200 0.25 M Na2S & Na2SO3 306 (Chem, 2012)
CdSe/ZnS Visible NA 35 mM Triethanolamine 11,948 (Huang et al., 2012)
Ag2S-coupled ZnO/ UV–Visible 80 10 mL 5% glycerol 650.4 (Liu et al., 2013a)
ZnS
ZnIn2S4@CuInS2 Visible 50 0.25 M Na2SO3 & 0.25 M Na2S 1168 (Guo et al., 2020)
Pt-PdS/CdS Visible 60 0.1 M Na2S & 0.1 M Na2SO3 394 (Yang et al., 2012)
RGO/ZnO@ZnS UV–Visible 50 5% Glycerol 310 (Xitao et al., 2014)
Au@CdS Visible 8 0.1 M Na2SO3 & 0.1 M Na2S 383.6 (Ma et al., 2014)
CdS/ZnS Visible 100 0.1 M Na2SO3 & 0.1 M Na2S 2075 (Xie et al., 2014)
CdS/CdSe UV–visible 3.74 0.45 M Na2S 784 (Wang et al., 2014a)
CdS/ZnS UV–visible 5 0.3 M Na2SO3 & 0.3 M Na2S 68,600 (Reddy et al., 2018b)
Cu2S/TiO2 UV–visible 5 0.3 M Na2SO4 & 0.3 M Na2S 41,600 (Navakoteswara Rao et al.,
2019)
CdSe/TiO2 UV–visible 5 0.3 M Na2SO4 & 0.3 M Na2S 40,600 (Rao et al., 2020b)
CdS/NiO UV–visible 5 0.3 M Na2SO4 & 0.3 M Na2S 19,900 (Lakshmana Reddy et al.,
2018a)

is given in Table 1. the outer surface rather than or before being consumed by the electron-
It can be observed from the literature that there have been consid­ donors in the reaction. This in turn subsequently causes irreversible
erable works dedicated to the synthesis of photocatalytic materials with oxidation of surface-bound sulfide ions to sulfur and/or sulfate ions,
core/shell structure by keeping the photoactive material as core and thereby creating compositional instability in the materials and leading
photo-sensitive material as a shell. Later, it was evolved to have the to considerable declines in the photocatalytic process and stability.
core/shell structures based on their band edge positions to effectively Meanwhile, it should be noted that the separated holes in metal sulfides
facilitate the charge transfer at the interfaces. The selection of core and often will not be available for the recombination with electrons rather it
shell materials could be based on the requirements, where a range of accumulates on the surface. This essentially indicates that the electrons
materials including metals, metal oxides, chalcogenides, carbon, will be largely available for the photoreduction process. Nevertheless,
nonmetal-oxides have been employed as core and shell materials. The the accumulation of holes must be taken care of as it severely causes
properties of core/shell structures could be tunable based on the mate­ adverse effects.
rial as well as their morphology. As described above, a wide range of Under such circumstances, the construction of core-shell structures
combinations of core/shell materials have been developed such as comes handy, where the shell material inhibits the dissociation of
metal/metal, metal/metal oxides, chalcogenides/metal oxide, metal surface-ions in the core, thereby enhances the overall photocatalytic and
oxide/carbon, etc. Similarly, based on the morphological designs, stability properties of the materials. Notably, such protection becomes
different types of core/shell structures have been developed, which
include the designs such as small-core/thick-shell, large-core/thin-shell,
movable-core/shell, multi-core/shell structures. Furthermore, the shape
of the core and/or shell has also been varied as cubes, fibers, spiky,
feathery, hexagonal, etc. These interesting structures have also been
widely studied for photocatalytic applications. The construction of core/
shell structured photocatalysts is essentially to have an enhanced charge
separation in the system, photosensitization, etc., where the shell ma­
terial is also often used merely to protect the core-material from
chemical and physical modifications during the course of reactions.
Such aspects can be seen in the case of metal chalcogenides-based
photocatalysts.
Metal chalcogenides are realized to have better photocatalytic ac­
tivity as compared to oxides. However, the key drawback of metal
chalcogenides is their poor compositional stability, where they often go
through the photocorrosion process that degrades the chalcogenides
thereby ultimately reduces the overall photocatalytic efficiency as well
as the stability of the catalysts. The compositional instability is essen­
tially an intrinsic characteristic of metal chalcogenides, which should be
overcome to exploit their inherent potential properties for any given
application. Accordingly, in order to protect from the possible photo­
corrosion process, metal chalcogenides are often covered with shell
materials. For instance, the origin of photocorrosion can be explained in
metal sulfide such as CdS can be explained as follows; upon the incident
photons, the electrons and holes jump to the conduction band and Fig. 3. Schematic representation of various properties of core-shell structured
valence band, respectively, and get transferred to the surface. However, materials towards photocatalytic applications.
the problem is that the photo-induced holes tend to be accumulated on (Reprinted with permission from Ong et al. (2015), Copyright 2015, Royal
Society Chemistry) (Wang et al., 2015).

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V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 4. Schematic presentation of the general photocatalytic water splitting principle under the light irradiation.
(Reprinted with permission from Shanshan Chen et al. (2011), Copyright 2011, Nature) (Chen et al., 2017b).

possible even if both core and shell are formed using metal sulfides. For
instance, based on the band edges position of CdS-core and ZnS-shell,
the holes created in the VB of CdS-core will be rapidly accepted by
default-acceptors in ZnS-shell such as intrinsic defects due to interstitial-
sulfur or Zn-vacancies. This eventually enhances the recombination-
resistance and anti-photocorrosion properties in the CdS/ZnS core/
shell system. Interestingly, a core/shell system keeping Cd as core and
ZnO-CdS as the shell has been developed, where it is proposed that the
Cd-core channelize the photo induced electrons in CB of ZnO to
recombine with the holes in VB of CdS via the Z-scheme mechanism.
This essentially prolongs the lifetime of carriers in the system and en­
hances the photostability along with photocatalytic properties.
Through such intriguing mechanisms, the core/shell structures of
CdS/TiO2, CdS/ZnS, Cu2S/TiO2, CdSe/TiO2 and CdS/NiO demonstrated
H2 evolution at highest rates such 258,526, 68,600, 41,600, 40,600 and
19,900 µmol/g/h, respectively under the irradiation of UV–visible light
in vicinity of Na2SO4/Na2S (@0.3 M) as an effective electron donor (Rao
et al., 2018; Xitao et al., 2014; Ma et al., 2014; Xie et al., 2014; Wang
et al., 2014a). Similarly, the systems such as ZnO/ZnS-PdS, Ag2S-­
coupled ZnO/ZnS, and RGO/ZnO@ZnS yielded the H2 gas at the rate of
2141, 650, and 310 µmol/g/h, respectively when the glycerol was used
in the reaction medium under UV–visible light irradiation (Lakshmana
Reddy et al., 2018b; Liu, 2016; Huang et al., 2012). The CdSe/ZnS
core/shell produced the H2 at a rate of 1194 µmol/g/h in the reaction
solution of 35 mM triethanolamine under visible light irradiation (Rao
et al., 2020b). The other visible-light-driven systems such as CdS/ZnO,
ZnIn2S4@CuInS2, Pt-PdS/CdS, Au@CdS, CdS/ZnS lead to the production
of H2 gas at the rate of 354, 1168, 394, 383, 2075 µmol/g/h, respec­
tively in presence of Na2SO4/Na2S sacrificial agents (Yang et al., 2013b;
Liu et al., 2013b, 2013a; Chem, 2012; Guo et al., 2020). These observed
variations in H2 production efficiencies of these core/shell materials
were attributed to their synergistic properties that manifested due to the
core/shell structuring as compared to their single counterparts.
1.2. Benefits of core-shell morphology in photo-excitons separation and
corrosion resistance
Core-shell morphologies are the uniquely compatible structures for a
photocatalyst system in the nanoscale size range and they have pre­
vailed considerable attention recently owing to their attractive proper­
ties as well as their applications in photocatalysis (Chen et al., 2017b;
Shevchenko et al., 2008; Maeda et al., 2006; Co et al., 2014). Several
core-shell morphological nanostructures have been prepared by modi­
fying the cores along with the shell material to manifest tunable prop­
erties. These modified core-shells play crucial roles in photocatalytic
applications, which can be a promising solution for environmental
remediation abatement as they have superior photocatalytic stability
and recyclability along with an excellent interface charge transfer and

Fig. 5. Photocatalytic hydrogen reaction mechanism in the pristine Cu2S and Cu2S/TiO2 core/shell photocatalyst.
(Reprinted with permission from Navakoteswara Rao et al. (2019), Copyright 2019, Elsevier) (Navakoteswara Rao et al., 2019).

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V. Navakoteswara Rao et al.
Fig. 6. Graphical representation of group IV, II-V semiconductors and metal chalcogenides band edge potentials for photocatalytic hydrogen applications (Joe et al.,
2019).
(Reprinted with permission from Jeo et al. (2019), Copyright 2019, MDPI).
Fig. 7. Schematic representation of the various structural features of core-shell
nanostructure.
(Reprinted with permission from Wang et al. (2015), Copyright 2015, Willey)
(Wang et al., 2015).
light absorption as shown in Fig. 3. In the recent year, the developments
of core-shell nanoparticles with metals such as Pt, Pd, Zn, Ni, Au, Ag,
etc., or oxides/chalcogenides such as CdS, CdSe, ZnS, Cu2S, CuS, Bi2O3,
and In2O3, etc., as the core and TiO2, NiO, ZnS and oxynitrides as the
shell have created massive research interests in the area of photo­
catalysis and solar photovoltaics (Yang et al., 2013d; Bai et al., 2014;
Search et al., 2013).
1.3. Overview of metal chalcogenides
The compounds consisting of one chalcogen as anion and one elec­
tropositive cation in their structures are called chalcogenides and they
are referred to as oxygen family including sulfides, tellurides, and
selenide in their structures. Because of the different chemical behaviors
of oxygen in chalcogines, it is often excluded from the “chalcogenide”
family. Thus, sulfur (S), selenium (Se), and tellurium (Te) are the other
chalcogenides, which find considerable applications. In optoelectronic
devices, the S-based materials are widely used and Se-based materials
5
Journal of Hazardous Materials 415 (2021) 125588
find applications in the biomedical field for imaging. Apart from this,
they are also used in sensors and solar cells (Horiuchi et al., 2004; Li
et al., 2013a). Similarly, Te-based materials are widely used in infrared
detectors and memory devices. Except for noble gases, derivatives of
chalcogenide are well cognized for the main group elements. Mostly,
stoichiometry follows the classical valence trends as in CdS, CuS, CdSe,
SiS2, B2S3, and Sb2S3 (Xiao et al., 2018; Cooper et al., 2011; Zhou et al.,
2014; Xu and Zhao, 2018).
The majority of studied compounds for chalcogens are transition
metal chalcogenides, which include zinc (ZnS, ZnSe, ZnTe), cadmium
(CdS, CdSe, CdTe), MoS2, and mercury-based chalcogenides (HgCdTe)
as they form many structures with different stoichiometric composi­
tions. Among these, 1:1 and 1:2 stoichiometries are found to be simple
and effective. The Wurtzite structure makes them non-ionic and highly
covalent. In the first case, the diamond framework arises by the occu­
pancy of sulfide atoms in cubic symmetry and Zn2+ ions occupy half of
the tetrahedral holes. In the second case, viz., the Wurtzite structure, the
main atom connectivity is similar (tetrahedral), but the crystal sym­
metry is hexagonal. Nickel arsenide lattice is the third motive for tran­
sition metal chalcogenides, and in this, both metal and chalcogenides
having octahedral and trigonal prismatic coordination exist, respec­
tively. Mono-sulfides are a combination of minerals and ores such as
chalcopyrite’s (FeS) and pigments (CdS).
On the nature of boding configuration with transition metals, the
transition metal chalcogenides are again classified into mono- and di-
chalcogenides, where the formula for metal mono-chalcogenides
(MCs) is MC, where “M” is a transition metal and “C” is S, Se or Te
(one of the chalcogenides). On the other hand, the formula for metal
dichalcogenides (MDCs) is MC2, where “M” is transition metal and “C” is
S, Se, Te. Most MDCs exhibit semiconductor properties and are inves­
tigated as cathode materials for the secondary batteries (e.g., TiS2) (Xiao
et al., 2018; Li et al., 2014). As a catalyst and solid lubricant, MoS2 is
much investigated and has been the widely used material (Guo et al.,
2016; Li et al., 2016a; Kadam et al., 2015; Wang et al., 2017; Sun et al.,
2018). Typically, MDCs adopt either octahedral or trigonal prismatic
structure. There is a weak chalcogenide-chalcogenide bonding between
the layers, but on the other hand, there is a strong bonding between
metal and chalcogenide ligands. The materials with these counter­
pointing bond strengths made such materials to employ in intercalation
by the alkali metals, thereby tunable composition and properties can be
manifested in these types of materials (Cooper et al., 2011).
1.4. Focus of this review
Considering the above mentioned perspectives and what is known
from the recent literature, this review is mainly focused to shed lights on
V. Navakoteswara Rao et al.
Fig. 8. Nitrogen adsorption and desorption peaks of the (a) pristine CdSe and (b) CST-2 (CdSe/NiO) core/shell photocatalysts.
(Reprinted with permission, Copyright 2020, Willey) (Rao et al., 2020b).
Fig. 9. Types of core-shell photocatalyst for photocatalytic applications.
(Reprinted with permission, Copyright 2015, MDPI) (Abouelhamd et al., 2019).
the evolution of highly efficient and stable chalcogenides-based photo­
catalysts for H2 production under visible light, better photoexcitons
transfer through an interface, protection of chalcogenide through sur­
face coverage. Furthermore, a detailed survey has been made on the
classification of core-shell materials and the advantages of hierarchal
nanostructures for photocatalytic applications. It also explores various
parameters such as the effect of temperature, solution medium, catalyst
loading, optimization of shell thickness and core diameter, electron
donors, surfactants, and stability studies, which are essentially playing
key roles towards enhancing the photocatalytic properties and espe­
cially for H2 generation.
2. Principle of photocatalytic hydrogen generation
Photosynthesis is a natural phenomenon that exists in plants for the
direct generation of hydrogen from the sunlight, where the H2O and CO2
are converted into oxygen and carbohydrates in the presence of sunlight.
Based on the above phenomenon, artificial photosynthesis is a similar
technology that uses sunlight to convert water into H2 and O2 for the
generation of fuels (known as solar fuels), which aims to replicate the
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Journal of Hazardous Materials 415 (2021) 125588
natural photosynthesis using man-made materials. In general, the basic
water splitting mechanism of photocatalysis is based on the photoex­
cited charge carriers generated during the photocatalytic reaction.
Photocatalysis is a redox process in which the presence of a photo­
catalyst significantly accelerates the rate of a surface chemical reaction
under light irradiation. The photocatalyst is a semiconductor, which
generates photo-excitons during illumination of semiconductor parti­
cles, possessing sufficient potential for oxidation and reduction re­
actions, closely associated with the band-edge potential. In general,
there are three major steps implied in the process of photocatalytic
water splitting reaction on the semiconductor. These three steps include:
(i) generation of electrons (e-) and holes (h+) pairs inside the semi­
conductor particles by the absorption of the incident light, which is
having the exceeding bandgap energies of the semiconductor material;
(ii) the generated e- and h+ are promoted to conduction and valance
band, respectively and followed by the transfer to the interface of the
semiconductor particles; (iii) surface chemical reactions among these
carriers with different surrounding compounds (e.g., H2O); where the e-
and h+ to generate H2 and O2 as depicted in Fig. 4. It is also possible that
the recombination of e- and h+ that occurs on a very fast time scale may
V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

that satisfy the basic requirements (vide supra) and absorb a visible light
spectrum of solar light for water splitting reaction is limited. (ii) Inef­
fective utilization of photo-generated charge carriers that results in fast
recombination, (iii) Poor surface interface reactions between the pho­
tocatalysts and reactants in reaction suspension. Hence, researchers
have explored several semiconducting materials as well as a combina­
tion of materials and practiced new techniques and strategies to over­
come the above-mentioned problems.
Metal chalcogenides tend to be photo-corrosive in nature, which can
be overcome via core/shell photocatalysts as the shell material protects
the core-metal chalcogenide from the photocorrosion process (Chen
et al., 2017b). Recently, we have proposed a photocorrosion mechanism
(Fig. 5) by comparing the pristine Cu2S and Cu2S/TiO2 core-shell pho­
tocatalyst (Navakoteswara Rao et al., 2019). In this study, optical and
electrochemical properties were studied, where it was explained that
Cu2S generated the photo-excitons by absorbing UV–visible light and
resulted in major bulk/surface recombination besides photo-corrosion
properties. Minor electron/hole at the surface involves in-situ oxida­
tion and reduction reactions, resulting in H2 generation. On the other
hand, core/shell morphology effectively utilized the excitons for the
generation of H+ and its subsequent reduction to produce H2 gas. In
addition, the direct exposure of Cu2S to the reaction medium is restricted
by the core-shell structure, which reduced the recombination
significantly.
Fig. 10. Pictorial representation of the Step scheme Heterojunction electron
transfer reaction mechanism for photocatalytic applications.
2.1. Band edge potential
(Reprinted with permission from Xu et al. (2020b), Copyright 2020, Elsevier)
(Xu et al., 2020a).
In general, enhanced photocatalytic hydrogen evolution reaction
requires desirable band gap energy for efficient water splitting
make these carriers not to participating in any chemical reactions and
(>+1.23 eV). In addition, conduction and valence band potentials of the
processes, which fundamentally affects the overall photocatalytic
semiconductor play a vital role in H2O oxidation and proton reduction
efficiency.
reactions. For efficient light absorption, the bandgap structure should
In order to accomplish an effective photocatalytic system, the
allow to absorption of a wide spectrum of solar radiation. To satisfy
semiconductor photocatalyst materials must have an appropriate band
these conditions, photoelectrodes must have an effective charge trans­
gap, suitable band energy potential, i.e. the bottom level of the con­
port feature and durable characteristics under wide operating conditions
duction band shall be more negative than the reduction potential of
(acidic or basic electrolytes). In a semiconductor, the maximum redox
H+/H2 (0.0 V versus normal hydrogen electrode), while the top level of
potentials of the photogenerated electron-hole pairs are found by sur­
the valence band shall be more positive than the oxidation potential of
face band edge positions (Chauhan et al., 2019). In the space charge
O2/H2O (1.23 V). Although the photocatalytic water splitting process
region (SCR), the oxidation or reduction by holes or electrons requires
has been regarded as a sustainable approach for clean energy produc­
less power as compared to actual power due to energy loss in the SCR
tion, it still encounters some major issues as follows; (i) Photocatalysts
layer. The edge positions of the valence band (Ev) and conduction band

Fig. 11. Schematic representation of the (a) photocatalytic charge carriers transfer in between tungsten trioxide (WO3) and graphitic carbon nitride (g-C3N4) before
contact. (b) The internal electric field and band edge bending at the interface of g-C3N4/WO3 after contact. (c) The S-scheme charge transfer mechanism between
WO3 and g-C3N4 under light irradiation.
(Reprinted with permission from Fu et al. (2019), Copyright 2019, Elsevier) (Fu et al., 2019).

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V. Navakoteswara Rao et al.
Fig. 12. Pictorial representation of the formation of CdS/ZnS core/shell photocatalyst synthesized by single-step hydrothermal process.
(Reprinted with permission from Lakshmana Reddy et al. (2018a), Copyright 2018, Elsevier) (Reddy et al., 2018b).
(Ec) should satisfy the oxidation/reduction potential of water.
For a water-splitting reaction, the semiconductor can act as a pho­
toanode, but it should have the valence band maximum (VBM) below
the water oxidation potential and for the semiconductor to act as a
photocathode, conduction band minimum (CBM) should lie above the
potential of water reduction. Fig. 6 depicts the band edge position and
bandgap energy of several semiconductor materials concerning the
standard hydrogen electrode (SHE) and vacuum energy level (Joe et al.,
2019). It is noteworthy that the group III-V semiconductors including
GaAs, GaN, and GaInP2 having viable water reduction potential as
compared to the group IV materials.
2.2. Surface active sites and turnover frequency
The photocatalyst surface active sites play a vital role in the superior
photocatalytic performance. To assess such properties, the surface
characteristics of photocatalysts are widely measured by BET analysis
with N2 adsorption and desorption curves. Core-shell photocatalysts
tend to have a high specific surface area and the relevant properties as
displayed in Fig. 7 toward achieving the enhanced photocatalytic H2
evolution efficiencies.
Recently, through the N2 adsorption-desorption measurements, our
group has demonstrated the surface characteristics of TiO2 shell in
CdSe@TiO2 and CdSe nanocomposites (NC). As compared to pristine
CdSe, the CdSe@TiO2 core@shell showed high porosity and type IV
isotherm due to TiO2 wrapping on the CdSe core as depicted in Fig. 8(a,
b). The diameter of the CdSe core was found to be 21 ± 2 nm with
enhanced pore-size distribution, where the specific surface area of CdSe
NC, as well as the optimized CdSe@TiO2, was estimated to be 2.5 and
10.5 m2/g, respectively. The high surface area of CdSe@TiO2 indicated
the availability of a greater number of active catalytic sites on the shell
material that essentially triggered the composite towards the enhanced
hydrogen fuel generation. In addition, the turnover frequency of the
photocatalysts was also estimated to be 0.05018 s− 1. The turnover
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Journal of Hazardous Materials 415 (2021) 125588
frequency number is generally calculated as, Turnover frequency
(TOF) = Amount of product (mol)/(Amount of catalytic active sites x
time (s)).
3. Classification, synthesis, and properties of core-shell
nanocomposite photocatalysts
3.1. Classification of core-shell nanocomposite photocatalyst
Based on the valence and conduction band positions, core-shell
materials are classified into four types: (i) Type-I, (ii) Type-II, or
Reverse Type-II, (iii) Inverse Type-I and (iv) S-Type.
3.1.1. Type-I core/shell structures
In Type-I, the bandgap energy of the core materials is lower than the
shell materials. The valence and conduction band edges of the core
stretch out within the shell bandgap, which confines the charge carriers
within the core. Schematic representation displayed in Fig. 9 shows that
the valance band maximum (VBM) and conduction band minimum
(CBM) of the narrow bandgap (eg. CdSe core (1.74 eV)) comfortably lies
within the wide bandgap (eg. ZnS shell (3.42 eV)) material. In such type,
the separation energy will be less. Accordingly, as compared to the
uncoated CdSe, a slower radiative electron-hole recombination was
observed in the coated CdSe material validated by observing a slight red
shift in the PL emission spectrum (Chauviré et al., 2015; Shao et al.,
2014). Recently, Xie et al. reported the Type-I core-shell interaction in
mesoporous CdS/ZnS nanocomposite for having improved visible pho­
tocatalytic efficiency (Xie et al., 2014). Similarly, many researchers have
reported the development of metal chalcogenides with Type-I core-shell
interaction for the superior photocatalytic H2 performance (Xitao et al.,
2014; Joe et al., 2019; Chauviré et al., 2015).
3.1.2. Type-II core/shell structures
In Type II arrangement, the valence and conduction band edge of the
V. Navakoteswara Rao et al.
Fig. 13. Schematic representation of Cu2S/TiO2 core-shell photocatalyst synthesized using a two-stage method. (For interpretation of the references to color in this
figure legend, the reader is referred to the web version of this article.)
(Reprinted with permission from Navakoteswara Rao et al. (2019), Copyright 2019, Elsevier) (Navakoteswara Rao et al., 2019).
Fig. 14. The preparation of core-shell fibers by co-axial electrospinning method
with two co-axial capillaries with schematic representation.
(Reprinted with permission, Copyright 2018, Springer) (Alghoraibi and Alo­
mari, 2019).
core is either lower or higher than the band edges of the shell material.
From Fig. 9, for instance, the bandgap energy of ZnTe is around 2.26 eV
and the bandgap of CdSe is 1.74 eV, in which the least partition energy
of e- and hole will happen when the hole is limited in the ZnTe core
valence band, and electron is confined in the CdSe shell conduction
band. As indicated by the arrow (Fig. 9), the energy difference between
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Journal of Hazardous Materials 415 (2021) 125588
the two occupied states fixes the wavelength emission, which must have
lower energy than the individual bandgap.
3.1.3. Inverse Type-I core/shell structures
In this type, the shell will have a lower bandgap as compared to the
core material, and also, the edges of valence and conduction band of the
shell material lie within the core material (Fig. 9). In the shell, if the
charge carriers are localized, then there is an occurrence of energy
separation in the material.
3.1.4. Step-scheme (S-type)core/shell structures
In this type of S-scheme based core/shell photocatalysts as depicted
in Fig. 10, the band gap alignment thereby the photo-redox efficiency
requires the integration of two semiconductors; one with enhanced
oxidation properties (WO3 and Fe2O3) and the other with enhanced
reduction properties (CdS, MoS2, CuS, and TiO2). Interestingly, this type
of core/shell structure presents hot topics in the field of photocatalysis.
Fig. 11 reveals the charge transfer mechanism in Step-scheme from
oxidation photocatalyst to reduction photocatalyst. In this mechanism,
upon the solar light irradiation, both the oxidation and reduction pho­
tocatalysts get excited, where the electrons excited in the oxidation
catalyst and the holes formed in the reduction catalyst accumulate at the
interfacial space charge region. Meanwhile, the holes in the oxidation
catalyst (at VB) and electrons in the reduction catalyst (at CB) are effi­
ciently promoted to the surface and involve in the photo-redox reaction
towards performing the photocatalytic process. Consequently, many
researchers have developed such S-type heterojunction photocatalysts
for the effective photocatalytic hydrogen generation via water splitting
(Sun et al., 2018; Chauhan et al., 2019; Joe et al., 2019; Chauviré et al.,
2015; Shao et al., 2014; Preethi and Kanmani, 2018; Xu et al., 2015;
V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 15. Core-shell and hollow fibers prepared by coaxial electrospinning showing (a) the TEM image showing the core-shell structure, (b) the SEM image showing
the hollow structure, ((c) TEM image showing the single-wall hollow structure, (d) SEM image showing the core-shell structure obtained using altered tri-axial
electrospinning (Insert: the photograph of spinneret), (e) TEM image showing the core-shell structure via air-blowing-assisted coaxial electrospinning [In inset
blow-assisted set: (A) inner capillary, (B) middle capillary, (C) outer bracket for air blow). (f) General set-up of (c) with different solutions in each layer.
(Reprinted with permission from Wang et al. (2020), Copyright 2020, Atlantis press (Wang et al., 2020).

Abouelhamd et al., 2019; Fu et al., 2019; Xu et al., 2020a; Li et al., 2020;
Di et al., 2020).
3.2. Synthesis methods for core-shell photocatalysts
Generally, depending upon the material’s chemical and physical
characteristics, the core-shell photocatalysts are prepared in two
different routes:(i) single-step method and (ii) two steps method.
3.2.1. Single-step method
In this method, both the shell and core precursors are combined in
the presence of heat treatment for a particular time to form the core/
shell structures. These methods include the hydrothermal, solvothermal,
and aqueous phase methods. In our group, we have accounted for the
production of CdS/ZnS materials by the hydrothermal method for
photocatalytic H2 production. Fig. 12 shows schematics depicting the
formation of CdS/ZnS core/shell nanostructures. In this process, firstly,
the unvarying dispersion of ZnO, Cd2+,and S2- was obtained by making
the solution mixture consisting of CdCl2, ZnO, and thiourea aqueous
solutions. During the hydrothermal process, S2- ions from thiourea are
combined with Cd2+ ions and leads to the constitution of the CdS so­
lution. Through the nucleation and growth process, the excess S2- ions
react with ZnO to form ZnS through replacement reaction. It is noticed
that the CdS forms first and then shell ZnS was forming onto the CdS
surface. According to the Gibbs free energy variation, Zn2+ hydration
ions are higher than the Cd2+ ions, where Cd2+ ions reacted with S2- to
form CdS/ZnS core/shell nanostructure.
3.2.2. Two-step method
In the two-step method, at first, synthesis of the core material fol­
lowed by wrapping of shell material will be performed using the
solution-based method. To wrap the core with a shell, either the
surfactant or non-surfactant mediated synthesis can be employed.
Recently, we have prepared the Cu2S/TiO2 by a facile synthetic two-step
method to achieve the core-shell nanostructures. Fig. 13 reveals the step-
wise formation of Cu2S@TiO2 core-shell. At first, the preparation of
Cu2S core was carried out as follows: (i) dissolution of copper precursor
in ethylene diamine solution (served as the structure-directing agent),
which turns colorless and then into blue color indicated that the copper
ions are attached to ethylenediamine (en) in the form of Cu(en)2; (ii)
addition of thiourea resulted in a change of color from blue to pale green
due to the formation of surface urea complex; (iii) upon continuous
magnetic stirring, the formation of black Cu2S got adsorbed with the
reaction byproducts onto the hexagonal and spheroids morphologies;
(iv) heterostructures of hexagonal and spheroidal shapes with the
negative surface charge was obtained. Secondly, during the preparation
of a thin layer of TiO2 shell, (v) a positive ion layer was formed on the
Cu2S particles by dispersing it in tri-sodium citrate solution; (vi) TTIP
was hydrolyzed to form Ti(OH)4 anions and subsequently get adsorbed
onto the positive layer of Cu2S; (vii) a thin layer of TiO2 was constituted
on Cu2S besides the adsorption of reaction by-products, and (viii) finally
the formed product was dried to obtain the clean surface of Cu2S@TiO2
core-shell structure.
3.2.3. Electrospinning method
The electrospinning process has been explored for several years and
used to prepare a range of core-shell complex structures. This can have a
range of supplementary functionalities or improved performance as
compared to monolithic fibers from the mono-axial spinning process.
Accordingly, to date, the most widely studied processes are coaxial, side-
by-side (or Janus), and triaxial electrospinning. The coaxial spinneret
was one of the four spinnerets developed by Cooley in 1902, and the
other three include (i) traditional single fluid spinneret, (ii) air-assist
spinneret, and (iii) the spinneret with rotating the valve distributor.

10
V. Navakoteswara Rao et al.
Fig. 16. Schematic representation of the interaction of core materials with different surfactants (a) anionic, (b) cationic, and (c) non-ionic.
The coaxial electrospinning (or electro-spray) has been further
improved during 2002–2003. Moreover, the modified coaxial electro­
spinning technology is vastly explored and widely adopted in the elec­
trospinning process. Therefore, electrospinning can be a promising
technique to prepare the core-shell structured fibers Fig. 14 reveals the
preparation of core-shell nanofibers with two co-axial capillaries, where
the first co-axial capillary run with core material precursor and second
co-axial capillary syringe will contain the shell material to be deposited
on the surface of core and Fig. 15(a)–(f) displays the SEM and TEM
images with different magnifications (Liu et al., 2020; Peng et al., 2020;
Xiang et al., 2020; Szilágyi et al., 2013; Doğan et al., 2019; Wang et al.,
2020).
4. Various factors influence the efficiency of core/shell
photocatalytic materials
The construction of core-shell architecture has three major chal­
lenges such as mono-dispersion of core materials, intact interface con­
tact with shell layer, and uniform wrapping of the core with shell
materials. Similarly, literature exploration also accounts that the factors
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Journal of Hazardous Materials 415 (2021) 125588
such as nature of precursors or precipitating agents and its concentra­
tion, type of solvent, pH of the reaction solution, nature of the surfac­
tants, volume of solution, mixing rate, and reaction temperature
(Chaudhuri and Paria, 2012; Gawande et al., 2015; Li et al., 2009) can
also significantly affect the photocatalytic attributes of the core/shell
structured materials. The ionic charge of surfactants such as anionic,
cationic, non-ionic or amphoteric nature plays a vital role towards
achieving the formation of mono-dispersed core-shell nanostructures.
The interactions of surfactant with the core materials are vital to achieve
uniform core-shell structures (as depicted in Fig. 16(a)–(c)) for the su­
perior photocatalytic performances.
4.1. Effect of morphology
The dimension dependent various morphologies of photocatalyst as
shown in Fig. 17 brings a critical function in photocatalysis owing to the
momentum of an electron in the particular dimension/direction, where
it facilitates an effective redox reaction (Chem, 2012). In general, the 1D
(nanorods, nanowires) nanostructures show better performance as
compared to 0D nanoparticles, 2D nanobelts, nanosheets, and 3D
V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Table 2
Essential role organic and inorganic sacrificial agents for enhanced photo­
catalytic H2 generation.
Name of the Sacrificial agent H2 generation Ref.
photocatalyst used (mmol h− 1 g− 1
cat)

Cu/Ag quantum Glycerol & 47.2 (Reddy et al.,

dots on TiO2 Methanol 16.1 2017a)
nanotubes Ethanol 20.7
Ethylene glycol 24.9
Crude glycerol 15.2
CdS/TiO2 Na2S/Na2SO4 258.5 (Rao et al., 2018)
CdS/ZnS Na2S/Na2SO3 68.7 (Reddy et al.,
2018b)
CdS/NiO Na2S/Na2SO3 19.9 (Lakshmana
Reddy et al.,
2018c)
Cu2S/TiO2 H2S containing 41.5 (Navakoteswara
effluent Rao et al., 2019)
CdSe/TiO2 Na2S/Na2SO4 40.6 (Rao et al., 2020b)
Pt-Au/TiO2 Methanol 7.2 (Rosseler et al.,
2010)
TiS2 and TaS2- Benzyl alcohol 9.4 (Gupta et al.,
CdS 2014)
CdS+ZnS/Fe2O3 Na2S & Na2SO3 15.4 (Luo et al., 2009)
Ni(OH)2/TiO2 Crude glycerol 4.7 (Reddy et al.,
nanotubes 2018a)
CdSe(QDs) Na2SO3 9.1 (Holmes et al.,
Fig. 17. Schematic representation of morphology of CdS nanostructures. 2012)
MoS2/CdSe Na2S/Na2SO3 0.9 (Frame et al.,
(Reprinted with permission from Cheng et al. (2018), Copyright 2018, Royal
2010)
Society Chemistry) (Cheng et al., 2018).
Pt-CdS (NH4)2SO3 13.2 (Yao et al., 2013)
CuS/NiO Na2S/Na2SO4 10.7 (Vempuluru et al.,
2020)
ZnS/NiO Na2S/Na2SO4 162.1 (Rao et al., 2021)

Fig. 18. Photocatalytic hydrogen production of the effect catalyst loading for
optimized Co4S3/CdS nanocomposite photocatalyst under simulated solar light
irradiation.
(Reprinted with permission, Copyright 2020, Elsevier) (Ravi et al., 2019).

nano-spherical materials (Liu et al., 2012; Kumar et al., 2017; Kar et al.,
2009; Wang et al., 2010). Recently, Cheng et al. (2018) reviewed the
CdS-based photocatalysts on their different morphological features and
reported their effect on the catalytic performance, governed by the
surface-active site as well as surface area due to their morphologies.
Fig. 19. Pictorial representation of the reaction mechanism for TiO2 shell
thickness influence on the photocatalytic H2 evolution.
(Reprinted with permission, Copyright 2020, Willey) (Rao et al., 2020b).

operating temperature, but polymerization reaction requires low tem­

4.2. Temperature effect
In the formation of nanostructures, the common parameter that
largely determines the kinetics of the reaction is the operating temper­
ature during the synthesis. In general, for the sol-gel reactions, the
temperature is not important, whereas it is the most important param­
eter in the reactions such as polymerizations, precipitation, and de­
compositions. Notably, thermal decomposition requires a higher
perature for better conversion. However, precipitation reaction is
marginally different. It is divided into three steps for particle formation:
(i) nucleation, (ii) growth, and (iii) agglomeration. These steps deter­
mine particle size and the nature of chemical reaction determines the
nucleation process, whereas it may be an exothermic or endothermic
reaction, wherein the growth process can be more complicated. The
nucleation process also depends on the atom diffusion from bulk to the

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V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 20. HRTEM image and SAED pattern of (a, f) CdSe, (b, g) CST-1, (c, h) CST-3, (d, i) CST-4, and (e, j) CST-5 core-shell photocatalyst.
(Reprinted with permission, Copyright 2020, Willey) (Rao et al., 2020b).

Fig. 21. TEM images of (a–c) pristine ZnS at different magnifications ZC-3, (d) ZCNS-1, (e) ZCNS-2, (f) ZCNS-3, (g,h) ZCNS-4, (i) HR-TEM image of lattice structures
withplane distance of 0.31 nm corresponds to (111) plane of ZnS.
(Reprinted with permission from Rao et al. (2021), Copyright 2021, Elsevier) (Rao et al., 2021)

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V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Table 3 Ravi et al. tuned the loading of CuO/NiO@TiO2 nanocomposite catalyst

Literature reports on the optimization of shell thickness of various core/shell from 5 to 100 mg, among which, the 20 mg catalyst concentration
structured photocatalysts and their photocatalytic H2 efficacy. showed the highest rate of H2 performance in their study (Ravi et al.,
Photocatalyst Shell Light Rate of H2 Ref. 2019).
thickness source evolution
(nm) (µmol/h/gcat)
4.5. Sacrificial agents
CdS@G@TiO2 3 Solar light 1510 (Zubair et al.,
2020)
CdS-TiO2 6.3 UV–visible 2,58,526 (Rao et al., 2018)
The selection of the most suitable sacrificial reagent is a very
ZnO-ZnS 12 UV–visible 2608.7 (Sang et al., 2011) important criterion for the effective photocatalytic H2 generation. This is
CdS-ZnS 15 UV–visible 3400 (Reddy et al., because the sacrificial reagents encounter a crucial part in the
2018b) improvement of photocatalytic activity depending upon the chemical
CdSe-TiO2 3–8 UV–visible 40.6 (Rao et al., 2020b)
and physical properties of the photocatalyst as well asthe nature of the
Cu2S-TiO2 12–16 UV–visible 41.2 (Navakoteswara
Rao et al., 2019) sacrificial reagents. Generally, organic sacrificial agents and inorganic
ZnO-CdS 20.2 UV–visible 2800 (Wang et al., sacrificial agents are the two main classifications of sacrificial reagents.
2010) In this context, several organic compounds such as alcohols, hydrocar­
CdS-TiO2 10–30 Visible 4080 (El-Maghrabi bons, and organic acids have been employed as hole scavengers (i.e. as
light et al., 2018)
CdSe-CdS 8.4 UV–visible 33 (Zhu et al., 2012)
e-donors) for the photocatalytic H2 generation reaction. Specifically,
CdS-MoS2 10–20 Visible 416.4 (Kadam et al., methanol, ethanol, glycerol, crude glycerol, tri-ethanolamine, and lactic
light 2019) acid have often been used as sacrificial reagents. The introduction of a
CdS@CoSx 3.5–40 Visible 3920 (Zhu et al., 2020) small percentage of sacrificial reagents as an e- donor to respond irre­
light
versibly with the photo-generated valence band holes can raise the
CdS@MoS2 5 Visible 493.1 (Han et al., 2017)
light photocatalytically generated electrons, where the hole detachment ef­
ficiency eventually results in more eminent quantum efficiencies.
Similarly, various inorganic sacrificial reagents, for instance, Na2S,
surface. At increased temperatures, the diffusion coefficient increases, Na2SO3, Na2SO4, Na2S2O3, Na2S2O8 have also been utilized for photo­
but the nature of the reaction determines the product concentration. On catalytic hydrogen generation, where these inorganic salts used to been
the other hand, for an endothermic reaction, the rate of reaction en­ employed as hole scavengers (i.e. as e- donors). Importantly, these
hances with an increase in temperature and vice versa for an exothermic inorganic salts tend to inhibit the photocorrosive nature of the metal
reaction. sulfides (CdS, ZnS, etc.) and contribute to enhancing the photocatalytic
H2 generation. Especially, sodium sulfides, sodium sulfites, and sodium
4.3. Solution medium sulfate are often used as a sacrificial reagent for sulfide based photo­
catalysts. Table 2 shows the effect of various sacrificial agents employed
The formation of core-shell morphology depends on reaction in­ in the photocatalytic H2 generation reactions.
termediates and the pH of the reaction solution. Furthermore, changing
the pH of reaction media considerably alters the reduction and precip­ 4.6. Optimization of shell thickness
itation reactions. The highest reduction potential compound can be
reduced by a lower reduction potential compound by simply oxi­ The thickness of the shell demonstrates a considerable role in having
dization, which can take place in a redox reaction. In addition, the pH of improved photocatalytic H2 yield owing to the increased charge carrier
the medium determines half-cell reduction potential. Therefore, for a detachment and protection from the photocorrosion. It has been
controlled reaction to take place and surface modification to happen, a accounted that the thickness of the shell around 2–20 nm showed effi­
favorable pH is recommended. The pH determines the surface charge of cient excitons separations for the improved photocatalytic H2 generation
the system, where as the hydrophilic core requires polyelectrolyte (PE) (Yang et al., 2013b; Tsai et al., 2014). Domen et al., (Sakamoto et al.,
modifiers to obtain uniform shell coating. From the above discussions to 2009) examined the effects of shell thickness and concluded that
increase the impelling force for the uniform coating of the shell, the 3–20 nm shell thickness range could be optimum for enhanced photo­
solution pH seems to encounter a major function towards adsorbing the catalytic H2 production. Xu and co-workers studied the metal@TiO2
shell material onto the surface of the core material. (where metal = Au, Pd, and Pt) hierarchical nanohybrid with tunable
ultra-thin shells, which exhibited enhanced H2 production (Zhang et al.,
4.4. Catalyst loading 2011). Recently, our group (Reddy et al., 2018b) reported a superior
photocatalytic H2 production by utilizing CdS/ZnS and concluded that
It is widely encountered that the physicochemical properties such as both controlling the core diameter as well as the thickness of the shell
adsorption and desorption with the reactant solution tend to show significantly influence the effectiveness of the photocatalytic process.
exceptional photocatalytic properties, which largely depends upon the Recent reports (Rao et al., 2018; Lakshmana Reddy et al., 2018a) also
concentration of catalyst present in the reaction medium (Lakshmana reveal that the optimal shell thickness for instance in CdS/TiO2 and
Reddy et al., 2018c; Praveen Kumar et al., 2013). Based on a literature CdS/NiO core/shell photocatalysts improves the reaction efficiency
survey, a few photocatalysts have been optimized to be 3 mg and besides the inhibition of photo-corrosion. For instance, Fig. 19 shows the
meanwhile, there are about 10, 20, 30 and 50 mg of photocatalyst have changes in the concentration of titanium tetraisobutoxide (TTIB) from
also been reported as the ’optimized’ concentration towards achieving 0.4 to 1.8 mL lead to having the TiO2 shell with different (increasing)
the enhanced photocatalytic hydrogen generation (Fig. 18). Recently, shell thickness as supported by the TEM figures as depicted in Fig. 20. It

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V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 22. TEM images of the core C5Z3 core-shell photocatalyst (a–f) diameter increases with changes in synthesis time.
(Reprinted with permission from Lakshmana Reddy et al. (2018a), Copyright 2018, Elsevier) (Reddy et al., 2018b).

15
V. Navakoteswara Rao et al.
Fig. 23. Optimization of sacrificial reagent for CPN-2 photocatalyst.
(Reprinted with permission from Navakoteswara Rao et al. (2019), Copyright
2019, Elsevier) (Navakoteswara Rao et al., 2019).
was thus concluded that shell thickness of 4–15 nm exhibits an efficient
light transfer from shell to the core and showed better photocatalytic H2
activity. Similarly, in our recent work, we have demonstrated the
ZnS/NiO core/shell structure with varying shell thicnkness as shown in
Fig. 21(a)–(i), where the photocatalyst with optimized shell thicnkness
showed the highest rate of hydrogen production (Rao et al., 2021)
Recent reports on fine-tune optimization of shell thickness of various
core/shell structured photocatalysts and their H2 production efficiency
are listed in Table 3.
4.7. Optimization of core diameter
As similar to the controlling of shell thickness, controlling the size of
the core is also an important parameter in constructing the core/shell
materials for enhanced photocatalytic H2 generation. In this direction,
we have examined CdS/ZnS core/shell nanostructure, where optimiza­
tion of the core diameter was carried out by changing the reaction time
from 2 to 6 h. Among these, the core/shell prepared at 4 h reaction time
(Fig. 22) showed the better hydrogen production rate due to the
controlled and optimum core-to-shell size, which eventually resulted in
a better light penetration in the core surface and generation of more
number of charge carriers for the enhanced photocatalytic H2 produc­
tion (Reddy et al., 2018b).
4.8. Effect of electron donors
Researchers have also reported different electron donors as hole
capturing reagents. Depending upon the nature of the photocatalysts,
different types of scavengers are typically used for photocatalytic
oxidation. For example, metal chalcogenides-based photocatalysts
generally require include lactic acid, Na2S, Na2SO4, and Na2SO3 as
scavengers as it reduces the overall charge recombination in the system
as well as photocorrosion in the system. In this context, we (Nav­
akoteswara Rao et al., 2019) have reported various organic and inor­
ganic sacrificial reagents along with their optimizations in
photocatalytic H2 generation as shown in Fig. 23. Among our findings,
Na2S and Na2SO4 showed a higher rate of H2 production owing to the
better absorption and desorption properties of the catalyst as well as
control over the photo-corrosion from light irradiation.
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Journal of Hazardous Materials 415 (2021) 125588
4.9. Stability studies
Enhancing the photocatalyst quality and stability is a crucial but
significant achievement in the development of photocatalysts. In this
direction, it is found that the metal chalcogenides-based core/shell
photocatalysts show superior photocatalytic stability for long-term
usage owing to the shell material that protects the core from the pho­
tocorrosion as well as other surface-mediated screening effects.
Recently, Guo et al. examined the MoS2, Au@MoS2, and Au@MoS2-ZnO
core/shell systems, where their photocatalytic experiments showed a
superior H2 performance (Fig. 24) due to the excellent stability rendered
by the core/shell structure (Guo et al., 2016). Similarly, El-Maghrabi
et al. reported (El-Maghrabi et al., 2018) the CdS/TiO2@Pt meso­
porous (0-D, 1-D) core-shell nanostructures, which exhibited a superior
reusable photocatalytic H2 yield under the natural solar light, wherein
the authors accomplished four cycles with each of 6 h. The synthesized
photocatalysts showed consistent H2 production efficiency due to the
core-shell structuring of the photocatalyst. Similarly, from our recent
study on the ZnS/NiO core/shell photocatalytic system (Rao et al., 2021)
the recyle ability of the photocatalyst with optimized shell thinkness was
investigated for five cycles under 1.5 G air mass filter, where it showed a
consistent rate of H2 generation of 3.42 mmol h− 1 g− 1cat as shown in
Fig. 25(a). Further, this recycled ZnS/NiO core/shell photocatalyst was
collected and wasted with ultra-pure water and absolute ethanol.
Interestingly, from the obtained TEM image (Fig. 25(b)) of this recycled
photocatalyst showed that the core/shell morphology was not found to
be affected and no significant changes were observed in their structure.
Such observation revealed that the synthesized core/shell photocatalyst
was stable and structurally efficient.
5. Summary and future perspectives
The present review addressed the classification of metal chalcogen­
ides and their application in photocatalytic H2 production. Based on the
bandgap engineering and subsequent alignments, the core-shell photo­
catalysts are categorized into three types: Type-I, Type-II, reverse Type-
I, and S-Type. The core-shell material preparation with the under­
standing of stepwise reaction mechanism followed by single or two steps
was discussed. Furthermore, a detailed study on the dimension and
morphology of the materials was considered, which included the 1D, 2D,
and 3D nanostructures that can greatly influence photocatalytic prop­
erties and reduce the charge carrier recombination due to their well-
defined nanostructures. The analysis of the photocatalytic parameters
such as opto-electrochemical, light-harvesting, surface area, optimiza­
tion shell thickness, core-diameter, the effect of the sacrificial reagent,
and recyclability of the core-shell photocatalyst was also discussed.
CSIR-CECRI manuscript communication number: CECRI/PESVC/
Pubs./2021-069.
CRediT authorship contribution statement
Vempuluru Navakoteswara Rao: Conceptualization, Writing -
original draft. Parnapalle Ravi: Methodology, Writing - original draft.
Marappan Sathish: Methodology, Validation. Manavalan Vijayaku­
mar: Resources, Formal analysis. Mohan Sakar: Visualization, Writing -
reviewing & editing. Mani Karthik: Writing - reviewing & editing.
Subramanian Balakumar: Writing - reviewing & editing. Kakarla
Raghava Reddy: Writing - reviewing & editing. Nagaraj P. Shetti:
Visualization. Tejraj M. Aminabhavi: Supervision, Writing - reviewing
& editing. Muthukonda Venkatakrishnan Shankar: Funding acquisi­
tion, Supervision, Writing - reviewing & editing.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
V. Navakoteswara Rao et al. Journal of Hazardous Materials 415 (2021) 125588

Fig. 24. Time-dependent photocatalytic H2 evolution over (a) MoS2, (b) Au@MoS2, and (c) Au@MoS2-ZnO, and H2 generation rate for (b) MoS2, (d) Au@MoS2, and
(f) Au@MoS2-ZnO.
(Reprinted with permission from Guo et al. (2016), Copyright 2016, Elsevier) (Guo et al., 2016).

17
V. Navakoteswara Rao et al.
Fig. 25. (a) Recycle ability of the ZnS/NiO core/shell photocatalyst for five cycles and (b) TEM image of the re-used ZnS/NiO core/shell photocatalyst.
(Reprinted with permission from Rao et al. (2021), Copyright 2021, Elsevier) Rao et al. (2021)
the work reported in this paper.
Acknowledgments
This work was supported by the Ministry of New and Renewable
Energy (MNRE), New Delhi, India (No. 103/227/2014-NT). The author,
V. Navakoteswara Rao gratefully acknowledges the Council of Scientific
Industrial Research (CSIR-SRF), New Delhi, India for financial support
through the fellowship 09/1076(0005)/2019-EMR-1 to carryout the Ph.
D. program.
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