processes

Review
Recent Trends in Graphitic Carbon Nitride-Based Binary and
Ternary Heterostructured Electrodes for Photoelectrochemical
Water Splitting
Ravindranadh Koutavarapu 1 , Shaik Gouse Peera 2 , Tae Gwan Lee 2 , Chimpiri Rao Myla 3, *, Dong-Yeon Lee 1, *,
Jaesool Shim 4, * and Suresh Kannan Balasingam 5, *,†

1 Department of Robotics and Intelligent Machine Engineering, College of Mechanical and IT Engineering,
Yeungnam University, Gyeongsan 712-749, Korea; [email protected]
2 Department of Environmental Science and Engineering, Keimyung University, Daegu 42602, Korea;
[email protected] (S.G.P.); [email protected] (T.G.L.)
3 Department of Physics, Andhra Loyola College, Vijayawada 520-008, Andhra Pradesh, India
4 School of Mechanical Engineering, Yeungnam University, Gyeongsan 712-749, Korea
5 Department of Materials Science and Engineering, Faculty of Natural Sciences, Norwegian University of
Science and Technology (NTNU), 7491 Trondheim, Norway
* Correspondence: [email protected] (C.R.M.); [email protected] (D.-Y.L.); [email protected] (J.S.);
[email protected] or [email protected] (S.K.B.)
† Current address: Graduate School of Energy and Environment (KU-KIST Green School), Korea University
(KU), Seoul 136-713, Korea.



Abstract: The graphitic carbon nitride (g-C3 N4 ) is a class of two-dimensional layered material. The


ever-growing research on this fascinating material is due to its unique visible light absorption,
Citation: Koutavarapu, R.; Peera, surface, electrocatalytic, and other physicochemical properties that can be useful to different energy
S.G.; Lee, T.G.; Myla, C.R.; Lee, D.-Y.; conversion and storage applications. Photoelectrochemical (PEC) water splitting reaction is one of the
Shim, J.; Balasingam, S.K. Recent promising applications of g-C3 N4 , wherein it acts as a durable catalyst support material. Very recently,
Trends in Graphitic Carbon
the construction of g-C3 N4 -based binary and ternary heterostructures exhibited superior PEC water
Nitride-Based Binary and Ternary
splitting performance owing to its reduced reunion of e-/h+ pairs and the fast transfer of charge
Heterostructured Electrodes for
carriers at the heterostructure interface. This review compiles the recent advances and challenges
Photoelectrochemical Water Splitting.
on g-C3 N4 -based heterostructured photocatalysts for the PEC water splitting reaction. After an
Processes 2021, 9, 1959. https://
doi.org/10.3390/pr9111959
overview of the available literature, we presume that g-C3 N4 -based photocatalysts showed enhanced
PEC water splitting performance. Therefore, it is believed that these materials have tremendous
Academic Editor: Bipro R. Dhar opportunities to act as durable catalyst support for energy-related applications. However, researchers
also considered several limitations and challenges for using C3 N4 as an efficient catalyst support
Received: 1 September 2021 material that must be addressed. This review article provides an overview of the fundamental
Accepted: 29 October 2021 principles of PEC water splitting, the current PEC water splitting research trends on g-C3 N4 -based
Published: 2 November 2021 binary and ternary heterostructured electrodes with respect to different electrolytes, and the other
key factors influencing their photoelectrochemical performance. Finally, the future research direction
Publisher’s Note: MDPI stays neutral with several recommendations to improve the photocatalytic efficiency of these materials is also
with regard to jurisdictional claims in
provided at the end.
published maps and institutional affil-
iations.
Keywords: g-C3 N4 ; binary and ternary heterostructures; photoelectrochemical water splitting;
hydrogen; photocatalyst

Copyright: © 2021 by the authors.

Licensee MDPI, Basel, Switzerland. 1. Introduction
This article is an open access article
With the rapid industrial developments and the expanding global population, the
distributed under the terms and
conditions of the Creative Commons
energy demand is constantly increasing, which has posed a significant threat to human
Attribution (CC BY) license (https://
life [1,2]. Furthermore, the extensive use of fossil fuels and industrial waste has led to
creativecommons.org/licenses/by/ a tremendous increase of greenhouse gases in the atmosphere [3,4]. On the other hand,
4.0/). renewable energy technologies such as wind, solar, and tidal energy have great potential

Processes 2021, 9, 1959. https://doi.org/10.3390/pr9111959 https://www.mdpi.com/journal/processes

Processes 2021, 9, 1959 2 of 26

for future generations [5]. Among these, solar energy is considered the most promising
one, due to its earth abundance and non-hazardous nature [6]. However, the wavelength of
solar illumination reaching the earth is greater than 340 nm, containing only a small portion
of UV light (<3%) and a large amount of visible light in the range of 400–800 nm. Therefore,
the design and synthesis of suitable visible-light active semiconductor materials having
a small bandgap are essential to harvest the abundant solar energy for photocatalytic and
other renewable energy-related applications [6,7].
Hydrogen is an attractive green fuel that can be used for many different applications,
such as heating, driving vehicles, and material refining [8,9]. Hydrogen has the poten-
tial to replace fossil fuels due to its highest energy density and the possibility to use in
internal combustion engines and fuel cells, which will be the future for emission-free trans-
portation [10–12]. Moreover, different water splitting techniques have been introduced
for hydrogen production, such as electrochemical, thermochemical, photocatalytic, pho-
toelectrochemical (PEC), and biological hydrogen production [13,14]. Among them, PEC
water splitting is one of the ways to utilize solar energy for hydrogen generation, which
can be further used for many other energy-related applications. [15,16]. Nevertheless,
hydrogen production via PEC water splitting is one of the promising methods due to its
safety factors, non-toxicity, and the final reaction that produces pure hydrogen and oxygen
without any byproducts [17,18].

1.1. Fundamental Concepts of Semiconductor-Mediated Heterogeneous Photocatalysis

Semiconductor-based nanostructures have received significant attention in recent
years for energy and environmental applications due to their cost-effective and straightfor-
ward synthesis process, and mainly they have nanograins of different sizes and different
kinds of heterostructured materials [19,20]. Further, the pristine semiconductor photocat-
alysts have exhibited minimal PEC water splitting abilities due to their rapid reunion of
charge carriers and having a lower surface area [21,22]. Thus, a combination of various
semiconductor materials with different morphologies can increase the performance in the
visible-light range of the solar spectrum. Moreover, the coupled heterostructured materials
with two or more components should have different energy levels that can play an essential
role in the interfacial charge transfer of the electron (e− ) and holes (h+ ) for the reduction
and oxidation of water molecules on the surface of heterostructured electrodes to achieve a
higher PEC water splitting activity [23,24].
In recent years, the graphitic carbon nitride (g-C3 N4 ) semiconductor-based binary
and ternary heterostructured materials have acted as promising photocatalysts for the
PEC water splitting and photocatalytic pollutant removal applications [25–27]. Therefore,
several investigations have been done on g-C3 N4 -based heterostructured photocatalysts
for the PEC water splitting application. Moreover, the heterostructured electrodes are
found as an attractive candidate due to their enhanced properties (such as larger surface
area, active reactive sites, and higher light absorption capacity) when compared to their
bulk counterparts [28,29]. In the case of a g-C3 N4 -based heterostructured electrode, the
suitable band edge potentials of the conduction band (CB) and valence band (VB) of dif-
ferent nanostructured semiconductor materials with various morphologies are combined
with g-C3 N4 , which could facilitate the charge transfer kinetics of photogenerated e− /h+
through the interfacial contact. Moreover, the solar-light active nanostructured materials
upon the irradiation generate reactive oxygen species, and it also assists in suppressing
the recombination rate of photogenerated e− /h+ pairs [30,31]. Therefore, in heterostruc-
tured photocatalysts, the assembly of heterojunction could improve the photocatalytic
reactions due to its extended absorption of light, synergistic interactions with facile charge
transportation, and the reduced recombination rate of charge carriers [32,33].

1.2. The Graphitic Carbon Nitride (g-C3 N4 ) Material

The g-C3 N4 is a kind of strong allotrope of carbon nitride family having a bandgap of
around 2.7 eV, and typically it is in the form of two-dimensional (2D) nanosheets comprising
Processes 2021, 9, x FOR PEER REVIEW 3 of 25

Processes 2021, 9, 1959 1.2. The Graphitic Carbon Nitride (g-C3N4) Material 3 of 26
The g-C3N4 is a kind of strong allotrope of carbon nitride family having a bandgap of
around 2.7 eV, and typically it is in the form of two-dimensional (2D) nanosheets com-
prising of tri-s-triazines interlayers [34]. The g-C3N4 is one of the graphite-like layered
of tri-s-triazines
structure interlayers
materials (shown in[34]. The g-C
Figure 3 N4 superior
1) with is one of prospects
the graphite-like layered
due to their easestructure
of avail-
materials (shown in Figure 1) with superior prospects due to their ease of availability, low
ability, low price, and environmental friendliness [35].
price, and environmental friendliness [35].

Figure 1.1.Two
Figure Twofundamental
fundamental structural
structural units
units of g-C
of g-C 3N4. Reprinted with permission from reference
3 N4 . Reprinted with permission from reference [36],
[36], Copyright 2018, Royal Society of Chemistry.
Copyright 2018, Royal Society of Chemistry.

Theg-C
The g-C33N
N44 molecular surface contains a large number of π-conjugated planar layers,
π-conjugated planar layers,
which
which have
have anan excellent
excellent complexing
complexing effect
effect with
with high
high stability,
stability, soso the
the material
material has
has been
been
used
used for
forphotocatalytic
photocatalyticand andPEC
PECapplications
applicationsin in
recent
recentyears [37].
years However,
[37]. because
However, of the
because of
utilization of only visible light, fastfast
recombination − /h
of eof + +pairs, low charge separation
the utilization of only visible light, recombination e−/h pairs, low charge separation
efficiency,
efficiency,andandthe
themoderate
moderatespecific
specificsurface
surfacearea,
area,ititcan
canprovide
providefewer
feweractive
activesites,
sites,which
which
reduces
reduces its
its effective
effectiveusage
usageas asaa pristine
pristinephotocatalyst
photocatalyst[38,39].
[38,39]. Thus,
Thus,in in order
ordertotoavoid
avoidthese
these
disadvantages,
disadvantages, the the design
designandandsynthesis
synthesisof ofg-C
g-C33NN44-based semiconductor
semiconductor heterostructures
heterostructures
with
with appropriate
appropriate photocatalytic
photocatalytic properties
properties could
could bebe an
an effective
effectiveapproach
approachfor forenhancing
enhancing
the PEC water splitting efficiency [40,41].
the PEC water splitting efficiency [40,41].

1.3.
1.3. Basic
Basic Principles
Principles of
of PEC
PEC Water
Water Splitting
Splitting
The
The increased accumulationofofgreenhouse
increased accumulation gases
greenhouse has
gases resulted
has in in
resulted a constant increase
a constant in
increase
the global average temperature, enabling a shift in perspective and redirecting the focus
in the global average temperature, enabling a shift in perspective and redirecting the focus
from carbon-based energy resources to carbon-free renewable energy technologies [42,43].
from carbon-based energy resources to carbon-free renewable energy technologies [42,43].
In this context, PEC water splitting has foremost importance, in that it generates4only
Processes 2021, 9, x FOR PEER REVIEW
In this context, PEC water splitting has foremost importance, in that it generates onlyofH272
H2 and O2 at two electrodes without any other polluting gases [5,44]. The schematic
and O2 at two electrodes without any other polluting gases [5,44]. The schematic repre-
representation of the PEC water splitting mechanism is presented in Figure 2.
sentation of the PEC water splitting mechanism is presented in Figure 2.

Figure 2. Schematic representation of PEC water splitting mechanism.

Figure2.2.Schematic
Figure Schematicrepresentation
representationof
ofPEC
PECwater
watersplitting
splittingmechanism.
mechanism.

Moreover, the PEC-based experiments are performed at room temperature, and the
semiconductor electrodes are fabricated using inorganic compounds, which are stable in
aqueous electrolytes. In contrast, organic-based semiconductor electrodes show poor sta-
Processes 2021, 9, 1959 4 of 26

Moreover, the PEC-based experiments are performed at room temperature, and the
semiconductor electrodes are fabricated using inorganic compounds, which are stable
in aqueous electrolytes. In contrast, organic-based semiconductor electrodes show poor
stability in PEC water splitting reactions [45,46]. The PEC water splitting device employs
quantum solar energy conversion materials in which the semiconductor absorbs incoming
photons, resulting in the electron–hole pairs generation process. The incident sunlight on
the photoanode excites electrons from the valence band to the conduction band, leaving
behind holes in the valence band of semiconductor material [47]. Further, the charge
separation typically occurs by the migration of carriers under the influence of the elec-
tric field, and the charge transfer occurs at the semiconductor/electrolyte interface. In
a photoelectrode, the minority carriers are transported to the electrochemical interface in
order to drive the reaction. For a photoanode, holes oxidize water molecules, and for
a photocathode, electrons reduce the H+ ions at the electrode surface [48].
For the past few years, solar-driven visible-light active semiconductor materials were
combined with g-C3 N4 , which showed a better PEC water splitting performance due to
their enhanced light absorption ability, robust synergistic interface, the enlarged surface
area, and the effective separation of e− /h+ pairs [49]. Furthermore, these g-C3 N4 -based
binary and ternary heterostructured electrodes with various morphologies can significantly
progress the movement of charge carriers at the electrode/electrolyte interface and, in turn,
enhance the PEC water splitting efficiency. However, despite these recent signs of progress,
critical reviews on g-C3 N4 -based binary and ternary heterostructured photoelectrodes for
the PEC water splitting reaction are still lacking. Therefore, this review summarizes the
different types of g-C3 N4 -based binary and ternary heterostructured photoelectrodes used
for PEC water splitting reaction, along with their advantages and limitations.

2. Importance of g-C3 N4 -Based Hybrid Heterostructured Electrodes

Generally, when the pristine g-C3 N4 is subjected to light, it absorbs photons and subse-
quently generates the photo-induced e− /h+ pairs. However, the excited electrons in the CB
are in a most unstable state and will tend to occupy the stable state, thus coming back to the
VB and recombining with photogenerated holes [50]. Therefore, to suppress the recombina-
tion of charge carriers and achieve maximum efficiency, g-C3 N4 should combine with other
semiconductor photocatalysts through the formation of heterostructured electrodes [51].
Recently, some approaches have been introduced to enhance the solar-driven visible-light
active photocatalytic performance of g-C3 N4 materials. For instance, the construction of
heterostructured electrodes with g-C3 N4 and other semiconductors, doping with metals
and non-metals, and the fabrication of mesoporous heterostructures [52–54]. Among them,
the construction of g-C3 N4 -based binary and ternary heterostructured electrodes exhibited
a superior PEC activity due to its reduced reunion of electron–hole pairs and the quick
transfer of charge carriers at the interface of the heterostructured electrodes. Furthermore,
while developing g-C3 N4 -based heterostructured electrodes, g-C3 N4 should associate with
both the visible and UV light-based semiconductor materials, which could enlarge the
absorption of the solar spectrum to the maximum range [55,56].

3. g-C3 N4 -Based Binary Heterostructured Photoelectrodes for PEC Water Splitting

The pristine g-C3 N4 material has limitations such as fast e− /h+ reunion rate, restricted
to visible-light absorption range, and the moderate surface area, which urges the devel-
opment of new approaches to enhance its applications [57,58]. To overcome the above
limitations and achieve greater efficiencies, g-C3 N4 -based binary heterostructures have
been constructed, and some of them are reported here. Binary heterostructures of g-C3 N4 ,
along with various concentrations of MnOx (2, 5, 7, 10, and 15%), were synthesized via
in-situ thermal decomposition method to enhance the PEC activity [59]. The XRD result
showed that the hexagonal phase of g-C3 N4 , the monoclinic phase of MnOx , and the
heterostructure formation did not affect the individual components. The morphology
results established that the irregular-shaped MnOx nanoparticles (NPs) dispersed over the
Processes 2021, 9, 1959 5 of 26

g-C3 N4 surface. The visible-light-harvesting ability of an electrode was enhanced by the

formation of heterostructure when compared to pristine samples. From the electrochemical
impedance spectroscopy (EIS) results, the 10% MnOx /g-C3 N4 heterostructured electrode
exhibited the lowest charge transfer resistance (Rct ) compared to the remaining samples.
Further, the 10% MnOx /g-C3 N4 heterostructured electrode showed a higher photocurrent
density (0.003 A cm−2 at 1.25 V vs. Ag/AgCl) than the remaining photoanodes. Thus,
the synergistic interactions among g-C3 N4 and MnOx can effectively progress the mobil-
ity of charge carriers and diminish the reunion of e− /h+ pairs, which enhances the PEC
performance. Wang et al. successfully constructed a core-shell g-C3 N4 @ZnO (CN/ZN) het-
erostructured electrode with different amounts of g-C3 N4 (0.01, 0.05, 0.10, 0.15, 0.20 g) using
a facile reflux technique [60]. The XRD results (Figure 3a) confirmed the hexagonal phase
of ZnO and the interlayer stacking of CN units with no impurity phases. The morphology
studies (Figure 3b) showed the heterostructure formation with an effective distribution of
ZnO NPs over the CN surface. When compared to the pristine ZnO, the visible-light absorp-
tion ability of the CN/ZN heterostructured electrode (Figure 3c) is enhanced through the
formation of heterostructures. The EIS results (Figure 3d) demonstrated that the CN/ZN-
0.15 heterostructured electrode exhibited the lowest charge-transfer resistance (Rct ) among
all samples. From the transient photocurrent (I-t) results (Figure 3e), the CN/ZN-0.15 pho-
toelectrode exhibited a sharp increase of photocurrent density with a quick photoresponse
than the other samples. Furthermore, the CN/ZN-0.15 photoelectrode provided a highest
photocurrent density at 1.5 V vs. SCE in 0.1 M Na2 SO4 electrolyte under visible-light
illumination. This improvement in the PEC water splitting activity (Figure 3f) is owed
to the core-shell morphology, higher light absorption capability, formation of synergistic
interfaces, and the facile charge carrier transport.
Xiao et al. successfully constructed a binary heterostructured electrode in which zero-
dimensional (0D) g-C3 N4 NPs covered over the one-dimensional (1D) TiO2 nanotube arrays
with an interfacial oxygen vacancy layer (CN/OV-TO). This heterostructured electrode
was synthesized using anodic oxidation followed by the reduction and vapor deposition
processes [61]. The visible-light-harvesting ability is improved substantially after forming
the heterostructure and oxygen vacancies (OV) associated with CN, TO, and CN/TO. The
structural and morphology investigations confirmed the formation of 0D/1D heterostruc-
tured electrodes. Further, the EIS results demonstrated that the constructed CN/OV-TO
heterostructured electrode exhibited the smallest Rct value among all prepared samples. In
addition, the photocurrent density of CN/OV-TO photoanode is around 0.72 mA cm−2 at
1.23 V Vs. RHE under visible-light illumination. This value is almost eight times higher
than the CN/TO heterostructured electrode without an interfacial OV layer. This enhanced
water splitting ability was attributed to the Z-scheme mechanism along with the interfacial
OV layer, which delays the reunion of e− /h+ pairs and endorses the facile charge carrier
transport mechanism. Reddy et al. constructed 1D ZnWO4 nanorods decorated over the
2D g-C3 N4 nanosheets using a facile hydrothermal synthesis method to enhance the PEC
water splitting reaction under solar light [62]. By the formation of the heterostructured
electrode, the solar light-harvesting capability was remarkably improved. The crystal phase
and morphology analysis confirmed the formation of the heterostructured electrode by the
successful decoration of ZnWO4 nanorods on the surface of g-C3 N4 nanosheets. Further,
the EIS results validated that the constructed 2D/1D heterostructured electrodes exhibited
the lowest Rct value when compared to pristine samples. Moreover, the photocurrent
density of the 2D/1D heterostructured electrode is almost 6.75 times and 3.31 times higher
than the pristine ZnWO4 and g-C3 N4 electrodes, respectively. Nevertheless, the 2D/1D
heterostructured electrode exhibited a very good stability and thus the formation of a bi-
nary heterostructured electrode could effectively improve the migration of charge carriers
with a lower charge transfer resistance and suppress the reunion of e− /h+ charge carriers.
Processes 2021, 9, 1959 6 of 26
Processes 2021, 9, x FOR PEER REVIEW 6 of 25

Figure
Figure 3.3. (a) XRD patterns,
(a) XRD patterns, (b)
(b)HRTEM
HRTEMimageimageofof15%CN@ZO
15%CN@ZOmaterial,
material,(c)(c) optical
optical absorption
absorption spec-
spectra,
tra, (d) Nyquist plots, (e) I-t curves, and (f) charge transfer mechanism of the CN@ZO heterostruc-
(d) Nyquist plots, (e) I-t curves, and (f) charge transfer mechanism of the CN@ZO heterostructured
tured electrode. Reprinted with permission from reference [60], Copyright 2017, Elsevier.
electrode. Reprinted with permission from reference [60], Copyright 2017, Elsevier.

AA novel
novelhybrid
hybridcarbon-doped
carbon-dopedCuO/g-C
CuO/g-C3N N4 (C-CuO/CN) heterostructured electrode
3 4 (C-CuO/CN) heterostructured electrode
was prepared using a facile one-step microwave-supported
was prepared using a facile one-step microwave-supported approach
approach to improve
to improve the PEC
the
performance
PEC performance underunder
visiblevisible
source source
[40]. The [40].crystal
Thephase results
crystal phase confirmed the formation
results confirmed the
of the monoclinic phase of CuO and the interlayer stacking of the CN
formation of the monoclinic phase of CuO and the interlayer stacking of the CN units. units. The morphol-
ogy results
The demonstrated
morphology that the CuO that
results demonstrated seems thetoCuO
be anseems
evenlyto dispersed
be an evenly micro-flowers
dispersed
consisting of intermixed ultrathin nanosheets and distributed
micro-flowers consisting of intermixed ultrathin nanosheets and distributed over the surface of over
CN. Thethe
photoluminescence spectra of C-CuO/CN heterostructured material
surface of CN. The photoluminescence spectra of C-CuO/CN heterostructured material showed a very weak
intensity
showed acompared
very weak tointensity
the CuO, compared
CN, and CuO/CNto the CuO, materials, and CuO/CN
CN, and this enhanced PL activity
materials, and
can
this be ascribedPL
enhanced to the significance
activity of carbonto
can be ascribed dopant, which influences
the significance of carbonlattice defects.
dopant, The
which
C-CuO/CN heterostructured
influences lattice defects. The electrode
C-CuO/CN exhibited the lowestelectrode
heterostructured charge transfer
exhibited resistance
the lowest of
3.48 kΩtransfer
charge cm−2 than the CuOof(18.53
resistance kΩcm
3.48 kΩ cm−−22 )than
and the
CuO/CN (7.69 kΩ
CuO (18.53 cm−2−)2 )electrodes.
kΩ cm and CuO/CN Fur-
thermore,
(7.69 kΩ cm −2photocurrent
the ) electrodes. density of the C-CuO/CN
Furthermore, electrode
the photocurrent is around
density of the −2.85 mA cm−2
C-CuO/CN
at 0 V vs. is
electrode RHE under
around visible
−2.85 −
mAsource,
cm at2 and0 Vit vs.
is around 227%visible
RHE under and 38% higher
source, and than
it isthe CuO
around
and
227%CuO/CN
and 38%electrodes,
higher than respectively.
the CuO and Thus, the carbon-doping,
CuO/CN influence of lattice
electrodes, respectively. Thus, thede-
fects, and the formation
carbon-doping, influence ofof
interfacial interactions
lattice defects, and thesignificantly
formation enhanced the interactions
of interfacial PEC perfor-
mance.
significantly enhanced the PEC performance.
Seza
Seza and
and co-workers
co-workers successfully
successfully constructed
constructed novelnovel photoelectrodes
photoelectrodes made made of of SnO
SnO22
NPs (various loading of 0.175, 0.6, and 11 g) g) decorated over the surface of porous g-C33N
decorated over the surface of porous g-C N44
nanosheets (CN/SN)
nanosheets (CN/SN)using usinga afacile
facilemicrowave
microwave synthesis
synthesis method
method [63].
[63]. TheThe XRDXRD re-
results
sults demonstrated
demonstrated thatCN/SN
that the the CN/SN heterostructured
heterostructured material
material exhibited
exhibited bothboth the 3g-C
the g-C N4
N4 3and
SnO2 phases. The morphology results showed the highly porous structure of CN
Processes 2021, 9, 1959 7 of 26

and SnO2 phases. The morphology results showed the highly porous structure of CN
nanosheets and the irregular shape of SnO2 NPs. The light absorption capacity of het-
erostructured CN/SN electrode enhanced towards the visible-active region compared to
the pristine samples. The CN/SN-0.175 heterostructured electrode exhibited the highest
specific surface area of 195 m2 g−1 compared to the other samples. From the linear sweep
voltammetry (LSV) results, the CN/SN-0.175 heterostructured electrode showed a pho-
tocurrent density of 0.033 mA cm−2 at 1.2 V vs. Ag/AgCl in 0.2 M Na2 SO4 electrolyte
under visible-light irradiation, and this photocurrent value is superior to the remaining
photoelectrodes. This enhanced PEC performance can be ascribed to the formation of
porous nanosheets, enhanced visible-light absorption ability, and the formation of the
interfacial heterostructure.
Novel binary g-C3 N4 combined with carbon nanotubes (CN/CT) heterostructured
film was systematically fabricated on the FTO substrate using a facile polycondensation
method to enhance PEC water splitting ability [52]. The structural and morphological
analysis evidence the formation of CN/CT heterostructured electrodes with synergistic
interfaces. As a result, the light-harvesting capacity systematically improved towards
the visible-active region by the development of heterostructure. Further, the EIS results
validated that the constructed CN/CT heterostructured electrode showed the lowest charge
transfer resistance of 6.5 × 105 Ω, and it is around 9.3 times higher than the pristine CN
electrode. The photocurrent density of the CN/CT heterostructured electrode showed
0.075 mA cm−2 at 1 V vs. Ag/AgCl under visible light, and it is around 11 times superior to
the pure CN photoanode. Thus, combing CN with CT significantly enhanced the electron
conductivity, light-harvesting ability, and the separation of charge carriers, which further
improved the PEC water splitting efficiency. Bakr and co-workers successfully constructed
a binary Z-scheme heterostructured electrode using α-Fe2 O3 nanotubes combined with
various concentrations (1, 2, and 3.75 wt.%) of ruptured tubular g-C3 N4 (FO/CN) using an
electrostatic self-assembly technique [64]. The XRD results revealed that both crystal phases
were presented in the FO/CN heterostructured electrode. The morphology results showed
that the α-Fe2 O3 nanotubes were anchored over the tubular g-C3 N4 , and the bandgap mod-
ification was detected for the FO/CN heterostructured material. The EIS results exhibited
the lowest charge transfer resistance value for FO/CN-1 sample. Furthermore, the FO/CN-
1 heterostructured electrode showed the highest photocurrent density of 0.0055 mA cm−2
at 1 V vs. SCE in 0.1 M Na2 SO4 electrolyte under sunlight. This improvement in the PEC
performance was due to the morphological interfaces, heterostructure formation, and quick
transportation of charge carriers.
Novel binary heterostructured electrodes made of BiOI nanoplates combined with
multilayered g-C3 N4 (BI/CN-M) and few-layered g-C3 N4 nanosheets (BI/CN-S) were
systematically synthesized using a simple solvothermal technique for the enhancement of
PEC water splitting reaction [65]. The XRD results showed the formation of the tetragonal
phase of BiOI and the interlayer stacking of CN, and both crystal phases have appeared in
the BI/CN-S heterostructured electrode. The morphology results demonstrated that the BI
nanoplates were decorated over the CN-S nanosheets, which confirmed the establishment
of the heterostructured material. Further, the FTIR and Raman spectra results evidently
showed the synergistic interactions among BI and CN materials. From the EIS results, the
BI/CN-S heterostructured electrode showed the lowest charge transfer resistance than the
pure BI, CN, and BI/CN-M electrodes. Moreover, the observed photocurrent density of
BI/CN-S heterostructured electrode was around 0.20 mA cm−2 at −0.5 V vs. Ag/AgCl in
0.1 M Na2 SO4 under visible-light irradiation, and the current density value was superior
to BI/CN-M (0.16 mA cm−2 ), BI (0.09 mA cm−2 ), CN-M (0.05 mA cm−2 ), and CN-S
(0.04 mA cm−2 ) electrodes. The enhanced water-splitting ability of the heterostructure
material was attributed to the enlarged light absorption ability, the diminished reunion of
charge carriers, and the synergistic trap passivation in the heterostructured electrode.
Liu and colleagues constructed the well-designed TiO2 nanotube arrays (TNTAs) and
dispersed the g-C3 N4 nanoparticles over TNTAs using anodic oxidation followed by calci-
Processes 2021,9,9,1959
Processes2021, x FOR PEER REVIEW 88 of
of2625

nation methods
calcination [66]. The
methods formation
[66]. mechanism
The formation of g-C3 Nof4 /TNTAs
mechanism (CN-TN)
g-C3N4/TNTAs heterojunction
(CN-TN) hetero-
was schematically
junction represented
was schematically in Figure 4a.
represented inThe crystallographic
Figure results showed
4a. The crystallographic the anatase
results showed
phase of TiOphase
the anatase 2 and interlayer
of TiO2 and stacking of g-C
interlayer 3 N4 , which
stacking of g-Csignificantly confirmed the
3N4, which significantly forma-
confirmed
tion of heterojunctions. The morphology results from Figure 4b–d showed
the formation of heterojunctions. The morphology results from Figure 4b–d showed3 that that the g-C N4
nanosheets covered the walls of the TiO nanotubes. From the LSV results
the g-C3N4 nanosheets covered the walls 2of the TiO2 nanotubes. From the LSV results (Fig- (Figure 4e),
the −2 and−2
urephotocurrent density of
4e), the photocurrent CN-TN
density electrode
of CN-TN was observed
electrode aroundaround
was observed 0.86 mA cmmA
0.86 cm
isand
nearly double
is nearly that that
double of pure TNTAs
of pure TNTAselectrode.
electrode.The
Thetransient
transient photocurrent
photocurrent(I-t) (I-t)results
results
(Figure
(Figure4f)4f)demonstrated
demonstratedthat thatthetheCN-TN
CN-TNheterojunction
heterojunctionelectrode
electrodeexhibited
exhibitedaasharpsharpin-in-
crease of photocurrent density with a quick photoresponse compared
crease of photocurrent density with a quick photoresponse compared to the as-prepared to the as-prepared
pristine
pristinesamples.
samples. The
Thecharge
chargetransfer
transferresistance
resistanceofofthe
theCN-TN
CN-TNheterojunction
heterojunctionelectrode
electrode
(Figure
(Figure 4g) was significantly reduced among the other samples underlight
4g) was significantly reduced among the other samples under lightillumination.
illumination.
Thus,
Thus,thetheformation
formationofofbinary
binaryheterojunction
heterojunctionbetween
betweeng-C g-C3 N
3N44 and
and TNTAs
TNTAs (Figure
(Figure4h) 4h)
could significantly
could significantly enhance the transportation of charge carriers and reduce
enhance the transportation of charge carriers and reduce the reunion the reunion of
photo-induced e − /h+ pairs, which in turn enhanced the PEC water splitting efficiency.
of photo-induced e /h pairs, which in turn enhanced the PEC water splitting efficiency.
− +

Figure4.4.(a)
Figure (a)Formation
Formationmechanism
mechanism ofof
CN-TN
CN-TN heterojunction, SEM
heterojunction, SEMimages
imagesof (b)
of TNTAs, (c) CN-TN
(b) TNTAs, (c) CN-
heterojunction, (d) TEM image of CN-TN heterojunction, (e) LSV curves, (f) I-t curves,
TN heterojunction, (d) TEM image of CN-TN heterojunction, (e) LSV curves, (f) I-t curves, (g) Nyquist(g)
plots, and plots,
Nyquist (h) charge transfer
and (h) mechanism
charge of the CN-TN
transfer mechanism of heterojunction. Reprinted with
the CN-TN heterojunction. permission
Reprinted with
permission
from referencefrom reference
[66], [66],
Copyright Copyright
2018, 2018, Springer.
Springer.
Processes 2021, 9, 1959 9 of 26

Liu and co-workers effectively fabricated the g-C3 N4 -coated Fe2 O3 nanoplatelets
(CN/FO) electrodes using the facile electrodeposition followed by chemical vapor deposi-
tion methods [67]. The morphology and structural results demonstrated the distribution of
g-C3 N4 nanoparticles over the surface of Fe2 O3 nanoplatelets. Further, the light-harvesting
ability was significantly enhanced after the formation of CN/FO heterostructuredelectrode,
and the PL intensity was diminished when compared to the pure CN and FO electrodes.
From the EIS analysis, the CN/FO heterostructured photoanode showed the lowest Rct
value compared to the remaining photoanodes. The photocurrent density of the CN/FO
heterostructured electrode showed around 0.78 mA cm−2 at 0.4 V vs. Ag/AgCl in 1.0 M
NaOH under visible light, and it is around 70 times higher than the pure FO photoan-
ode. Therefore, the introduction of CN over the surface of FO considerably enriched the
light-harvesting ability, separation of e− /h+ pairs, and quicker interfacial charge transfer,
which improved the water-splitting ability. Novel binary 2D/2D heterostructured electrode
composed of porous g-C3 N4 and BCN nanosheets (CN/BCN) was successfully fabricated
using a facile thermal polymerization technique [68]. The XRD results demonstrated that
both the crystal phases of CN and BCN were presented in the CN/BCN heterostructured
electrode. The morphology results showed that the porous CN nanosheets were anchored
over the BCN nanosheets. From differential reflectance spectroscopy (DRS) results, the
loading of CN towards BCN could substantially enhance the light-harvesting capability.
The charge transfer resistance of CN/BCN electrode was around 2.8 kΩ, which is 11 times
and five times lesser than CN and BCN electrodes, respectively. Further, the transient
photocurrent density of the CN/BCN electrode is higher than the individual CN and BCN
electrodes. Moreover, the CN/BCN heterostructured electrodes showed a photocurrent
density of 0.62 mA cm−2 at 0.62 V vs. Ag/AgCl in 0.1 M Na2 SO4 electrolyte under visible-
light illumination, which was around 8 and 3 times higher than the CN (0.08 mA cm−2 )
and BCN (0.21 mA cm−2 ) electrodes, respectively. Thus, the morphological 2D interfaces,
superior migration of charge carriers, and the separation of e− /h+ pairs significantly
enhanced the PEC water splitting performance.
Murugan and colleagues systematically fabricated a binary g-C3 N4 /TiO2 (CN/TO)
heterostructured electrode with different concentrations of CN (5, 10, 15, 20, and 25 wt.%)
using a facile in-situ soft template technique (Figure 5a) for the improvement of PEC water
splitting performance [69]. The XRD results (Figure 5b) confirmed the anatase phase of
TiO2 , the interlayer stacking of CN, and both the phases have appeared in the CN/TO
heterostructured electrode. The morphology results (Figure 5c,d) demonstrated that the TO
NPs were decorated over the CN nanosheets. From the EIS analysis (Figure 5e), the CN/TO-
20 photoanode showed the lowest Rct value than the remaining photoanodes. Furthermore,
the photocurrent density (Figure 5f–g) of CN/TO-20 heterostructured electrode was around
0.0723 mA cm−2 at 1.23 V vs. RHE in 1 M KOH electrolyte under visible-light and the
photocurrent density value was superior than the CN (0.00082 mA cm−2 ), TO (0.0366 mA
cm−2 ), CN/TO-5 (0.0472 mA cm−2 ), CN/TO-10 (0.0544 mA cm−2 ), CN/TO-15 (0.0632 mA
cm−2 ), and CN/TO-25 (0.0658 mA cm−2 ) electrodes. The enhanced water splitting ability
was accounted for their enlarged light absorption ability, the diminished reunion of charge
carriers, and synergistic interfacial effect in the heterostructured electrode. The same group,
Murugan and co-workers, successfully fabricated a binary combination of hierarchical
Bi2 MoO6 and various amounts (1, 3, 5, 7, 10, and 12 wt.%) of g-C3 N4 (BMO/CN) using a
solvothermal technique for the enhancement of PEC water splitting ability [70]. The XRD
results revealed the formation of the orthorhombic phase of BMO, the interlayer stacking
of CN, and both the phases have appeared in the BMO/CN heterostructured electrode.
The regulation of the bandgap was detected for the BMO/CN heterostructured electrode
compared to the pure samples, which enlarged the visible-light-harvesting capability. From
the EIS analysis, the BMO/CN-10 heterostructured electrode showed the lowest Rct value,
the photocurrent density of the BMO/CN-10 electrode was around 0.0212 mA cm− 2 at 1.23
V vs. RHE in 1 M KOH electrolyte under visible-light illumination, and the photocurrent
density value was about 28 and 7 times greater than the pristine CN and BMO electrodes,
Processes 2021, 9, 1959 10 of 26

respectively. Thus, heterostructure formation significantly enhanced the light-harvesting

Processes 2021, 9, x FOR PEER REVIEW separation of e− /h+ pairs, and quicker interfacial charge transfer, which progressed
ability, 11 of 27
the water-splitting ability.

Figure 5.
Figure 5. (a)
(a) Formation
Formation mechanism
mechanism of of CN@TO
CN@TO heterostructured
heterostructured material,
material, (b)
(b) XRD
XRD patterns,
patterns, (c)
(c) SEM
SEM
image of 20-CN@TO material, (d) TEM image of 20-CN@TO material, (e) Nyquist plots, (f)
image of 20-CN@TO material, (d) TEM image of 20-CN@TO material, (e) Nyquist plots, (f) LSV
LSV
curves, (g) I-t curves, and (h) charge transfer mechanism of the CN@TO heterostructured electrodes.
curves, (g) I-t curves, and (h) charge transfer mechanism of the CN@TO heterostructured electrodes.
Reprinted with permission from reference [69], Copyright 2020, Elsevier.
Reprinted with permission from reference [69], Copyright 2020, Elsevier.

Mohammad et al. successfully fabricated the novel heterostructured electrode using

Mohammad
different et al. successfully
concentrations (2 and 4 mM) fabricated
of SnO2 the
NPsnovel heterostructured
decorated electrode
over the surface using
of g-C 3 N4
different concentrations (2 and 4 mM) of SnO 2 NPs decorated over the surface of g-C3N4
nanosheets (CN/SN) via a simple hydrothermal method [71]. The XRD results confirmed
nanosheets
that both the(CN/SN)
crystal via a simple
phases of SNhydrothermal method
(tetragonal rutile [71]. and
phase) The XRD results
CN were confirmed
presented in
that both the crystal phases of SN (tetragonal rutile phase) and CN were
the CN/SN heterostructured electrode without any impurity phases. The FTIR and XPS presented in the
CN/SNestablished
results heterostructured electrode
the formation without heterostructured
of CN/SN any impurity phases. The FTIR
electrodes. The and XPS re-
visible-light-
sults established the formation of CN/SN heterostructured electrodes. The
harvesting ability was significantly enhanced after forming the CN/SN heterostructured visible-light-
harvestingand
electrode, ability was
the PL significantly
intensity enhanced compared
was diminished after forming thepure
to the CN/SN heterostructured
CN and SN materials.
electrode, and the PL intensity was diminished compared to
The CN/SN-4 mM heterostructured electrode demonstrated a higher specificthe pure CN andsurface
SN materi-
area
als. The CN/SN-4 mM heterostructured electrode demonstrated a higher specific surface
area of 181.54 m2 g−1 than the pure SN (181.13 m2 g−1) and CN/SN-2 mM (178.69 m2 g−1)
electrodes. From the EIS results, the CN/SN-4 mM heterostructured electrode showed the
lowest charge transfer resistance when compared to the pure CN, SN, and CN/SN-2 mM
electrodes. Furthermore, the photocurrent density of CN/SN-4 mM photoelectrode was
Processes 2021, 9, 1959 11 of 26

of 181.54 m2 g−1 than the pure SN (181.13 m2 g−1 ) and CN/SN-2 mM (178.69 m2 g−1 )
electrodes. From the EIS results, the CN/SN-4 mM heterostructured electrode showed the
lowest charge transfer resistance when compared to the pure CN, SN, and CN/SN-2 mM
electrodes. Furthermore, the photocurrent density of CN/SN-4 mM photoelectrode was
around 2.1 mA cm−2 at 1 V vs. Ag/AgCl in 0.2 M Na2 SO4 under visible-light and it was
around eight times higher than the pure SN electrode. The improved water splitting
performance was owing to the enhanced surface area, light absorption ability, diminished
reunion of charge carriers, and the synergistic effect in the heterostructured interface.
Kumar et al. successfully constructed heterostructured electrodes made of NaNbO3
nanofibers along with different concentrations (2, 4, and 8 wt.%) of g-C3 N4 nanosheets
(NNO/CN) using facile hydrothermal followed by chemisorption techniques (Figure 6a)
for better PEC water splitting performance [31]. The XRD results (Figure 6b) demonstrated
that both the crystal phases of CN (interlayer stacking) and NNO (orthorhombic phase)
were presented in the NNO/CN heterostructured electrode. The surface morphology
images (Figure 6c) confirmed the effective distribution of NNO nanofibers on the surface
of CN nanosheets. The DRS analysis (Figure 6d) showed that the visible-light-harvesting
ability was significantly enhanced in the NNO/CN heterostructure electrode. The EIS
results (Figure 6e) demonstrated that the NNO/CN-4 photoelectrode exhibited the lowest
Rct value, and the I-t results (Figure 6f) indicated that the NNO/CN-4 photoelectrode
showed a sharp increase of photocurrent density with a quicker photoresponse than the
other photoelectrodes. Moreover, the NNO/CN-4 photoelectrode showed a photocurrent
density of 12.5 mA cm−2 at 1 V vs. Ag/AgCl in 0.5 M NaOH electrolyte under visible-light,
which was around three-times higher than the pristine NNO electrode (4.3 mA cm−2 ).
Thus, the formation of heterostructured electrode (Figure 6g) significantly enhanced the
light-harvesting ability, separation of e− /h+ pairs, and quicker interfacial charge transfer,
which significantly improved the water-splitting ability.
A novel binary heterostructured electrode made of Bi2 WO6 quantum dots (QDs)
dispersed on the g-C3 N4 (CN/BWQ) was prepared by a simplistic in-situ hydrothermal
method [72]. The X-ray diffraction results confirmed the interlayer stacking of the CN units
and the orthorhombic phase of BW, even after the formation of a heterostructured electrode.
Furthermore, the morphological examination revealed that the BW QDs were uniformly
distributed over the surface of CN. When compared to the pristine samples, bandgap tuning
was observed for the CN/BWQ heterostructured electrode, which significantly enhanced
the visible-light-harvesting capability. Moreover, the CN/BWQ heterostructured electrode
demonstrated the lowest Rct value, the photocurrent density of CN/BWQ photoanode
was observed around 0.39 µA cm−2 at 1.23 V vs. RHE under visible-light illumination,
and the current density value was about 2.4 and 1.8 times higher than the pristine CN
and BWQ electrodes, respectively. Thus, forming a synergistic interfacial heterostructure
and the Z-scheme mechanism could significantly enhance the water-splitting activity. The
PEC performance of g-C3 N4 -based various binary heterostructured electrodes is presented
in Table 1.
 showed a sharp increase of photocurrent density with a quicker photoresponse than the
other photoelectrodes. Moreover, the NNO/CN-4 photoelectrode showed a photocurrent
density of 12.5 mA cm−2 at 1 V vs. Ag/AgCl in 0.5 M NaOH electrolyte under visible-light,
which was around three-times higher than the pristine NNO electrode (4.3 mA cm−2).
Processes 2021, 9, 1959 Thus, the formation of heterostructured electrode (Figure 6g) significantly enhanced the
12 of 26
light-harvesting ability, separation of e−/h+ pairs, and quicker interfacial charge transfer,
which significantly improved the water-splitting ability.

Figure 6. (a) Formation mechanism of NNO/CN heterostructured material, (b) XRD patterns,
(c) TEM image of NNO/CN heterostructured material, (d) optical absorption spectra, (e) Nyquist
plots, (f) I-t curves, and (g) charge transfer mechanism of the NNO/CN heterostructured electrode.
Reprinted with permission from reference [31], Copyright 2020, IOP.

Table 1. The PEC performance of g-C3 N4 -based binary heterostructured photoelectrodes.

Photocurrent
Synthesis Light
Photoelectrodes Potential (V) Electrolytes Density Ref.
Methods Sources
(mA cm−2 )
g-C3 N4 /ZnO Dip coating 0.5994 vs. RHE 0.5 M Na2 SO4 Visible 0.952 [73]
Pt/g-C3 N4 Dip coating 0 vs. RHE 0.1 M Na2 SO4 Solar −2.5 [74]
g-C3 N4 /CoP Impregnation 0.4 vs. Ag/AgCl 0.05 M Na2 SO4 Solar 0.15 [75]
g-C3 N4 /BiVO4 Hydrothermal 1.23 vs. RHE 1 M KOH visible 0.021 [76]
Electrophoretic
g-C3 N4 /CdS and chemical 0 vs. Ag/AgCl 0.5 M Na2 SO3 Visible 5.4 [77]
bath deposition
Liquid
g-C3 N4 /CNTs 0 vs. SCE 0.5 M Na2 SO4 Visible 0.0018 [78]
exfoliation
Pulsing
g-C3 N4 /SnO2 0.2 vs. Ag/AgCl 0.1 M NaOH Solar 1.8 [79]
electrophoresis
g-C3 N4 /BiVO4 Sol-gel -- vs. Ag/AgCl 0.1 M Na2 SO4 Solar 0.00046 [80]
Mixing
g-C3 N4 /InVO4 0.9 vs. Ag/AgCl 0.1 M Na2 SO4 Solar 0.013 [81]
calcination
g-C3 N4 /In2 S3 Wet chemical 1.5 vs. Ag/AgCl 0.1 M Na2 SO3 Visible 0.005 [82]
Electrophoretic
g-C3 N4 /Cu2 O −0.4 vs. Ag/AgCl 0.1 M NaNO3 Visible −1.38 [83]
deposition
Processes 2021, 9, 1959 13 of 26

Table 1. Cont.

Photocurrent
Synthesis Light
Photoelectrodes Potential (V) Electrolytes Density Ref.
Methods Sources
(mA cm−2 )
Phosphorus Near-
Sintering 1.2 vs. Ag/AgCl 0.5 M Na2 SO4 0.0014 [84]
doped g-C3 N4 infrared
g-C3 N4 /BiVO4 Electrodeposition 1.23 vs. RHE 0.5 M Na2 SO4 Solar 0.42 [85]
g-C3 N4 /CuO Co-precipitation 1.2 vs. Ag/AgCl – Visible 0.68 [86]
g-C3 N4 /MoS2 Solvothermal −0.4 vs. Ag/AgCl 0.1 M PBS Solar 0.037 [87]
g-C3 N4 @CuTi Hydrothermal 0.65 vs. Ag/AgCl 1 M KOH Visible 0.014 [88]
g- Magnetron
−0.3 vs. Ag/AgCl 0.1 M Na2 SO4 Solar 0.004 [89]
C3 N4 /LaFeO3 sputtering
Metal-assisted
g-C3 N4 @Si etching, and
1 vs. Pt 0.5 M Na2 SO4 Visible 0.316 [90]
NWs liquid atomic
layer deposition
Cobalt doped
Calcination Ag/AgCl 0.1 M Na2 SO4 Solar 0.058 [91]
g-C3 N4
g-C3 N4 @CoFe Solvothermal 0.2 vs. Ag/AgCl 1 M KOH Visible 0.196 [92]

4. g-C3 N4 -Based Ternary Heterostructured Photoelectrodes for PEC Water Splitting

Numerous efforts have been executed to fabricate g-C3 N4 -based binary heterostruc-
tured electrodes to overcome the constraints and improve the PEC water splitting ability.
However, the PEC performance is still limited and not up to the target of practical appli-
cations. To overcome these issues, g-C3 N4 -based complex compounds containing three
components have been introduced, and some of the results are discussed here. A novel
hybrid ternary anatase TiO2 /rutile TiO2 /g-C3 N4 (A/R/CN) heterostructured electrode
was prepared with different mass ratios of CN (20, 30, 40, 50, and 60 mg) using a facile
thermoset hybrid technique for the enhancement of water splitting performance [93]. The
XRD result confirmed the anatase and rutile phases of TiO2 and the interlayer stacking of
the CN units. The electron microscopy results validated that the TiO2 NPs were distributed
over the surface of CN, which signifies the formation of a heterostructured electrode. The
light-harvesting capacity systematically improved towards the visible region in the case of
the ternary heterostructured electrode. From the EIS results, the A/R/CN40 heterostruc-
tured electrode showed the lowest charge transfer resistance value than the pure P25, CN,
and A/R/CN20, A/R/CN30, A/R/CN50, and A/R/CN60 heterostructured electrodes.
Further, the photocurrent density of the A/R/CN40 photoanode was superior to the other
electrodes under solar light illumination. Thus, the formation of interfacial interactions
among the three components could improve the migration of charge carriers with more
separation, which further enhanced the PEC water splitting capability.
Reddy and co-workers have developed a novel ternary electrode made of CdS NPs
and Fe3 O4 nanocubes dispersed over the g-C3 N4 nanosheets (CS/FO/CN) using two-step
solvothermal techniques for the enhanced PEC water splitting performance [37]. The
morphology results demonstrated that the CdS NPs entered into the Fe3 O4 lattices and
were distributed on the surface of CN nanosheets. The XRD results confirmed the presence
of the hexagonal phase of CdS, the magnetite phase of Fe3 O4 , the interlayer stacking of
CN in CS/FO/CN heterostructured electrode, and the heterostructure formation did not
affect the individual phases. The CS/FO/CN electrode showed a superior specific surface
area of 40.022 m2 g−1 . Further, the CS/FO/CN ternary heterostructured electrode showed
enlarged light-harvesting performance. The charge transfer resistance of CS/FO/CN
ternary heterostructured electrode was significantly reduced when compared to CdS,
CN@CS, and CS@FO electrodes upon visible-light irradiation. The photocurrent density
of the CS/FO/CN ternary heterostructured electrode showed around 0.0238 mA cm−2 at
0.2 V vs. Ag/AgCl under visible-light irradiation, and it was around 5.95, 4.76, and 7.93
times higher than CdS, CN@CS, and CS@FO electrodes, respectively. This improvement in
the PEC performance was ascribed to the ternary interfacial charge transport, separation
efficiency of e− /h+ pairs, and the facile transportation of charge carriers.
Processes 2021, 9, 1959 14 of 26

Bhandary and colleagues fabricated a bimetallic AgNi alloy surrounded by g-C3 N4

nanosheets (CN/AgNi) electrodes using a facile one-pot solid-state heat treatment method
to improve the PEC water splitting capability [94]. The structural and morphological stud-
ies confirmed the heterostructure formation with a successful decoration of bimetallic AgNi
alloy over the surface of g-C3 N4 nanosheets. After the formation of the heterostructure,
the light absorption capability remarkably improved. Further, the EIS results confirmed
that the constructed CN/AgNi heterostructured electrode showed the lowest Rct value
among the pure samples. Furthermore, the CN/AgNi photoelectrode showed the highest
photocurrent density of 1.29 mA cm−2 at 1.0 V vs. Ag/AgCl in 1.0 M NaOH electrolyte
under visible light, and the value was more significant than the CN, CN/Ag, and CN/Ni
electrodes. Nevertheless, the CN/AgNi heterostructured electrode exhibited excellent sta-
bility, and thus the formation of a heterostructure could effectively improve the migration
of charge carriers with lower charge transfer resistance and suppress the reunion of e− /h+
pairs.
The novel ternary heterostructured electrodes of Ag3 PO4 /Ag2 MoO4 materials com-
bined with various concentrations (0.4, 0.8, and 1.2 wt.%) of multilayered g-C3 N4 nanosheets
(AP/AM/CN) were systematically fabricated using the in-situ co-precipitation technique
by Liu and colleagues [95]. The XRD results showed the formation of the cubic phase of
Ag3 PO4 and Ag2 MoO4 , the interlayer stacking of CN, and the ternary AP/AM/CN het-
erostructured electrode contained all three phases. The morphology results demonstrated
that both the AP and AM NPs were distributed over the surface of CN nanosheets, which
confirmed the establishment of the ternary heterostructured electrode. Further, the FTIR
and Raman spectra results evidently showed synergistic interactions among AP/AM and
CN interfaces. The visible-light-harvesting ability was considerably enhanced through the
formation of ternary AP/AM/CN heterostructured electrodes when compared to the CN,
AP, AM, and AP/AM electrodes. From the EIS results, the ternary AP/AM/CN photoan-
ode showed the lowest charge transfer resistance value when compared to the CN, AP, AM,
and AP/AM electrodes. Moreover, the photocurrent density of the ternary AP/AM/CN
photoelectrode was superior to the other samples under solar light illumination. Thus,
the enlarged solar light absorption ability could effectively diminish the reunion of charge
carriers and the dual Z-scheme charge carrier pathway that eventually enhanced the PEC
water splitting ability.
A novel hybrid ternary g-C3 N4 /Au-SnO2 QDs (CN/Au/SQD) heterostructured elec-
trode was prepared with different mass ratios of Au-SQD (10, 20, and 30 mg), using
calcination and sonication methods (Figure 7a) for the enhancement of PEC water splitting
performance [96]. The XRD results revealed the presence of the tetragonal phase of SnO2 ,
interlayer stacking of the CN units, and the metallic phase of Au. The electron microscopy
results (Figure 7b) confirmed that the Au-SQDs were distributed over the surface of CN,
which signifies the heterostructure formation. The light-harvesting efficiency (Figure 7c)
was systematically improved towards the visible region through the heterostructure for-
mation. The PL spectra (Figure 7d) of CN/Au/SQD heterostructured electrode showed a
very weak intensity compared to the SQD, CN, and Au-SQD samples. From the EIS results,
the CN/Au/SQD ternary electrode showed the lowest Rct value than the SQD, CN, and
Au-SQD electrodes. Furthermore, the CN/Au/SQD photoelectrode displayed the superior
photocurrent density (Figure 7e) of 0.0402 mA cm−2 at 1.0 V vs. Ag/AgCl in 0.1 M Na2 SO3
electrolyte under visible-light irradiation, and the value was significantly greater than the
SQD, CN, and Au-SQD electrodes. Thus, the fabrication of metal-semiconductor combined
with CN ternary heterostructured electrodes (Figure 7f) could improve the migration of
charge carriers with more separation efficiency, which further enhanced the PEC water
splitting performance.
Processes 2021,
Processes 9, x9,FOR
2021, 1959 PEER REVIEW 15 of 26 1

Figure
Figure 7.7.(a)
(a)Formation
Formation mechanism
mechanism of CN/Au-SQD
of CN/Au-SQD ternary
ternary heterostructured
heterostructured material,
material, (b) TEM (b) TE
age
imageofof
CN/Au-SQD
CN/Au-SQDheterostructured material,
heterostructured material, (c)(c) optical
optical absorption
absorption spectra,
spectra, (d) PL(d) PL spectra, (
spectra,
curves,
(e) and (f)and
LSV curves, charge transfer
(f) charge mechanism
transfer mechanismofofthetheCN/Au-SQD
CN/Au-SQD ternary heterostructured elect
ternary heterostructured
electrodes. Reprinted
Reprinted with permission
with permission from reference
from reference [96],[96], Copyright2020,
Copyright 2020, Elsevier.
Elsevier.

Li and co-workers systematically fabricated 0D Bi2 O3 NPs encapsulated with BiPO4

Li and
nanorods co-workers
that were distributedsystematically
over the surface fabricated
of g-C3 N4, 0D
whichBi2formed
O3 NPstheencapsulated
CN/BO/BP with
nanorods that were distributed
ternary heterostructured overthe
electrode using thefacile
surface of g-C3N4,method
hydrothermal whichfollowed
formed by the CN/B
calcination process [97]. The XRD results demonstrated that the ternary
ternary heterostructured electrode using the facile hydrothermal method followed b CN/BO/BP
heterostructured
cination processelectrode
[97]. The exhibited g-C3 N4 ,demonstrated
XRD results Bi2 O3 , and BiPOthat
4 phases, confirming
the ternary the
CN/BO/BP h
presence of individual components. The morphology results showed that the Bi2 O3 NPs
structured electrode exhibited g-C 3N4, Bi2O3, and BiPO4 phases, confirming the pre
were anchored over BiPO4 nanorods, and the binary BO/BP heterostructured material was
of individual
distributed overcomponents.
the surface of theTheg-Cmorphology results showed that the Bi2O3 NPs we
3 N4 nanosheets. When compared to pure samples,
chored
the lightover BiPO4efficiency
absorption nanorods, of and the binary heterostructured
the CN/BO/BP BO/BP heterostructured material was d
electrode enhanced
towards the visible region. From the EIS analysis, the ternary CN/BO/BP
uted over the surface of the g-C3N4 nanosheets. When compared to pure samples, the photoanode
exhibited the lowest
absorption Rct value
efficiency compared
of the CN/BO/BPto the pure CN, BO, BP, CN/BP,
heterostructured BO/BPenhanced
electrode electrodes. toward
From the LSV results, the CN/BO/BP photoanode showed a photocurrent density of 0.095
visible region. From the EIS analysis, the ternary CN/BO/BP photoanode exhibite
mA cm−2 at 1.25 V vs. Ag/AgCl in 0.1 M Na2 SO4 electrolyte under solar light irradiation,
lowest Rct value
and the value compared
was 2.4 to the
and 1.3 times puretoCN,
superior the BPBO,andBP, CN/BP,
BO/BP BO/BP
electrodes, electrodes. Fro
respectively.
LSV enhanced
This results, the
PEC CN/BO/BP
performance photoanode showed
could be ascribed a photocurrent
to the formation of thedensity of 0.095 mA
interfacial
heterostructure
at with the Z-scheme
1.25 V vs. Ag/AgCl in 0.1 Mprocess,
Na2SOwhich hinders the
4 electrolyte recombination
under solar lightofirradiation,
charge an
carriers and higher solar-light absorption ability.
value was 2.4 and 1.3 times superior to the BP and BO/BP electrodes, respectively
enhanced PEC performance could be ascribed to the formation of the interfacial h
structure with the Z-scheme process, which hinders the recombination of charge ca
and higher solar-light absorption ability. Chaudhary et al. have developed a novel te
Processes 2021, 9, 1959 16 of 26

Chaudhary et al. have developed a novel ternary heterostructured electrode consist-

ing of the TiO2 NPs with carbon nanotubes that dispersed over the g-C3 N4 nanosheets
(TO/CN/CNT) using a facile hydrothermal method [98]. The XRD results (Figure 8a) con-
firmed the anatase phase of TiO2 , the graphitic nature of CNT, and the interlayer stacking of
CN. The morphology results (Figure 8b) displayed that the TiO2 NPs and CNTs were deco-
rated on the surface of CN nanosheets. Further, the TO/CN/CNT ternary heterostructured
electrode showed an enlarged light-harvesting performance. The Rct value (Figure 8c) of
the TO/CN/CNT ternary heterostructured electrode was significantly reduced compared
to the TO, CN, and TO/CN electrodes under visible-light illumination. The photocurrent
density (Figure 8d) of the TO/CN/CNT ternary electrode showed 2.43 mA cm−2 at 0.6 V
vs. Ag/AgCl in 0.5 M Na2 SO4 electrolyte under visible-light, and the current density value
was around 6.4, and 3.2 times higher than the CN, TO/CN photoelectrodes, respectively.
Thus, the formation of interfacial interactions among the three components (Figure 8e)
could effectively improve the migration of charge carriers with more separation, which in
turn enhanced the PEC water splitting efficiency.
Si and co-workers systematically fabricated graphdiyne (GDY)-anchored g-C3 N4 /NiFe-
layered double hydroxide (CN/GDY/NF) electrode via the facile hydrothermal method [99].
The XRD results revealed that CN, GDY, and NF crystal phases were presented in the
CN/GDY/NF heterostructured electrode without any impurity phases. Further, the FTIR
and XPS results confirmed that the heterostructured material consisted of individual com-
pounds. The CN/GDY/NF heterostructured material presented a higher specific surface
area of 208.75 m2 g−1 than the pure CN (126.32 m2 g−1 ), GDY (95.03 m2 g−1 ), and NF
(42.63 m2 g−1 ) materials. The visible-light-harvesting ability was significantly enhanced
after forming the CN/GDY/NF heterostructured electrode, and the PL intensity was di-
minished compared to the pristine CN, GDY, and NF samples. From the EIS results, the
CN/GDY/NF photoelectrode showed the lowest Rct value than the pure CN, GDY, and
NF electrodes. Furthermore, the photocurrent density of ternary CN/GDY/NF photoelec-
trode was observed around 0.178 mA cm−2 at 1.4 V vs. RHE under visible light, and the
photocurrent density value was around 45 times higher than the pristine CN electrode. The
enhanced water splitting activity was ascribed to the formation of synergistic interactions
among the ternary components, which emphasized the visible-light absorption ability and
quick transfer of charge carriers with lower charge-transfer resistance.
Gopalakrishnan et al. adopted the spin-coating technique and successfully fabricated
the heterostructured electrode in which SrTiO3 NPs covered on the surface of g-C3 N4
nanosheets and coupled with silicon nanowires (ST/CN/Si) [100]. The crystallographic
analysis confirmed the formation of ST, CN, and Si phases in the ST/CN/Si heterostruc-
tured electrode without any impurity phases. The morphology results demonstrated
the uniform distribution of ST nanoparticles and Si nanowires on the surface of g-C3 N4 ,
which confirmed the formation of a synergistic interfacial heterostructure. Further, the
light-harvesting ability was significantly enhanced towards the visible region through the
formation of a ternary ST/CN/Si heterostructured electrode. From the EIS analysis, the
ST/CN/Si photocathode exhibited the lowest charge transfer resistance than the pure CN,
ST, Si, and CN@Si electrodes. The photocurrent density of the ST/CN/Si heterostructured
electrode showed around 28 mA cm−2 at 0.8 V vs. RHE in 0.5 M Na2 SO4 electrolyte under
visible light, and this current density value was superior to the other electrodes. Therefore,
the introduction of Si nanowires and ST nanoparticles on the surface of CN considerably
enriched the light-harvesting ability, separation of e− /h+ pairs, and quicker interfacial
charge transfer, which significantly progressed the water-splitting ability.
 pared to the TO, CN, and TO/CN electrodes under visible-light illumination. The photo-
current density (Figure 8d) of the TO/CN/CNT ternary electrode showed 2.43 mA cm−2 at
0.6 V vs. Ag/AgCl in 0.5 M Na2SO4 electrolyte under visible-light, and the current density
value was around 6.4, and 3.2 times higher than the CN, TO/CN photoelectrodes, respec-
Processes 2021, 9, 1959 17 of 26
tively. Thus, the formation of interfacial interactions among the three components (Figure
8e) could effectively improve the migration of charge carriers with more separation, which
in turn enhanced the PEC water splitting efficiency.

Figure 8. (a) XRD patterns, (b) TEM image of TO/CN/CNT heterostructured material, (c) Nyquist
plots, (d) LSV curves, and (e) charge transfer mechanism of the TO/CN/CNT ternary heterostruc-
tured electrode. Reprinted with permission from reference [98], Copyright 2020, Elsevier.

To enhance the utility of visible-light and diminish the reunion of charge carriers, a
novel fluorine-doped, chlorine-intercalated g-C3 N4 combined with various concentrations
of BiOI (10, 25, 57, and 75%)-based CNF-Cl/BI heterostructured electrodes was prepared
using a facile in-situ hydrothermal technique by Alam and co-workers [101]. The XRD
results confirmed the interlayer stacking of the CN units and the tetragonal phase of BI even
after the formation of a CNF-Cl/BI heterostructure. The morphology results demonstrated
that the BI nanoplates were uniformly covered on the surface of the CNF-Cl electrode.
The bandgap tuning was observed for the CNF-Cl/BI heterostructured electrode when
compared to pure samples, which significantly enhanced the visible-light absorption ability.
From the EIS results, the CNF-Cl/BI50% heterostructured electrode exhibited the lowest Rct
value than the remaining samples. Moreover, the photocurrent density of CNF-Cl/BI50%
photoanode was observed around 1.28 mA cm−2 at 1.23 V vs. RHE under visible-light
illumination, and the value was around 4.6 and 3.2 times higher than the CNF-Cl and BI
Processes 2021, 9, 1959 18 of 26

electrodes, respectively. Thus, the formation of synergistic interfaces, improved charge

separation, and the enlarged light-harvesting ability significantly enhanced the PEC water-
splitting performance.
Wu et al. systematically fabricated a novel Bi2 MoO6 -Ru binary heterostructured mate-
rial anchored on the surface of g-C3 N4 (BMO/Ru/CN) using a facile hydrothermal method
(Figure 9a) [102]. The XRD results (Figure 9b) demonstrated that all the crystal phases of
BMO, Ru, and CN were presented in the BMO/Ru/CN heterostructured electrode without
any impurity phases. Further, the peak shift of XPS confirmed the formation of ternary
BMO/Ru/CN heterostructured material. The visible-light-harvesting ability (Figure 9c)
was significantly enhanced after the BMO/Ru/CN heterostructure formation, and the PL
intensity was diminished compared to the BMO, CN, BMO/Ru, Ru/CN, and BMO/CN
samples. The morphology results (Figure 9d and e) revealed the uniform distribution of
BMO microspheres and Ru NPs on the surface of CN. From the EIS results (Figure 9f),
the BMO/Ru/CN heterostructured electrode showed the lowest Rct value than the BMO,
CN, BMO/Ru, Ru/CN, and BMO/CN electrodes. Furthermore, the photocurrent density
of ternary BMO/Ru/CN photoelectrode was around 1.0 mA cm−2 at 1.4 V vs. Ag/AgCl
under visible light, and the obtained photocurrent density was approximately 25 times
higher than the BMO/CN electrode. The enhanced water splitting performance (Figure
9g) was ascribed to the formation of synergistic coupling among the ternary components,
which emphasized the visible-light absorption ability and facile transportation of charge
carriers with a lower Rct value.
Patnaik and colleagues successfully synthesized the various concentrations (2, 4,
6, and 8 wt.%) of Cu-promoted MoO3 /g-C3 N4 (Cu/MO/CN) hybrid heterostructured
electrode using the in-situ pyrolysis followed by the impregnation techniques [103]. The
XRD results confirmed that the interlayer stacking of the CN units, the orthorhombic phase
of MoO3 , and the heterostructure formation did not influence the individual phase. The
morphological investigation inferred that the irregular-shaped MoO3 nanocrystals and
Cu nanoparticles dispersed on the g-C3 N4 surface. Further, the visible-light absorption
ability was improved by forming the heterostructure, and the distribution of Cu NPs was
confirmed by the occurrence of a surface plasmon resonance band. From the EIS results, the
2% Cu/MO/CN heterostructured electrode exhibited the lowest charge-transfer resistance
value among other samples. Further, the 2% Cu/MO/CN heterostructured electrode
showed a photocurrent density of around 5.1 mA cm−2 using 0.5 M Na2 SO4 electrolyte
under visible-light illumination, which was higher than the other electrodes. Thus, the
synergistic interactions having rich-oxygen vacancies could effectively improve the mobility
of charge carriers and diminish the reunion of electron/hole pairs, which enhanced the
PEC performance. The PEC performance of g-C3 N4 -based various ternary heterostructured
electrodes is presented in Table 2.
 Processes
Processes 9, x9, FOR
2021,
2021, 1959 PEER REVIEW 19 of 26 18 of 25

Figure 9. (a)
Figure 9. Formationmechanism
(a) Formation mechanism of the
of the BO/Ru/CN
BO/Ru/CN ternary
ternary heterostructured
heterostructured material,
material, (b) XRD (b) XRD
patterns,
patterns, (c) optical absorption spectra, (d) TEM image, (e) HRTEM image of BO/Ru/CN heterostructured hetero-
(c) optical absorption spectra, (d) TEM image, (e) HRTEM image of BO/Ru/CN
structured material,
material, (f) Nyquist (f) Nyquist
plots, plots,
and (g) charge and (g)
transfer charge of
mechanism transfer mechanism
the BO/Ru/CN of heterostructured
ternary the BO/Ru/CN ternary
heterostructured electrode. Reprinted with permission from reference [102], Copyright
electrode. Reprinted with permission from reference [102], Copyright 2019, American Chemical Society. 2019, Amer-
ican Chemical Society.

2. The PEC
Table Patnaik performance
and of g-C
colleagues 3 N4 -based ternary
successfully heterostructured
synthesized photoelectrodes.
the various concentrations (2, 4, 6,
and 8 wt.%) of Cu-promoted Synthesis
MoO3/g-C3N4 (Cu/MO/CN) hybrid Light
heterostructured
Photocurrent elec-
Photoelectrodes Potential (V) Electrolytes Density Ref.
trode using the in-situ pyrolysis
Methods followed by the impregnation techniques
Sources
(mA cm )− [103].
2 The XRD
results confirmed
ZnO/Au/g-C3 N4
that the
Thermalinterlayer
vapor stacking
−0.5 vs. RHE
of the CN units,
0.2 M Na2 SO4
the
Solar
orthorhombic
−0.29 [104]
phase of
condensation
MoO 3, and the heterostructure formation did not influence the individual phase. The mor-
g-C3 N4 /Pt/ZnO Spin coating 0.5 vs. Ag/AgCl 0.5 M Na2 SO4 Solar 0.12 [105]
phological investigation inferred that the irregular-shaped MoO3 nanocrystals and Cu na-
noparticles dispersed on the g-C3N4 surface. Further, the visible-light absorption ability
was improved by forming the heterostructure, and the distribution of Cu NPs was con-
firmed by the occurrence of a surface plasmon resonance band. From the EIS results, the
2% Cu/MO/CN heterostructured electrode exhibited the lowest charge-transfer resistance
value among other samples. Further, the 2% Cu/MO/CN heterostructured electrode
Processes 2021, 9, 1959 20 of 26

Table 2. Cont.

Photocurrent
Synthesis Light
Photoelectrodes Potential (V) Electrolytes Density Ref.
Methods Sources
(mA cm−2 )
g-C3 N4 /Ti-Fe2 O3 Electrodeposition 0.23 vs. Ag/AgCl 1.0 M NaOH Visible 2.55 [106]
g-C3 N4 /TiN-NFG Ultra-sonication 0.11 vs. RHE 0.5 M Na2 SO4 Solar −0.196 [107]
Hydrothermal, chemical
TiO2 @g-C3 N4 /Co-Pi bath deposition, 1.23 vs. RHE 0.1 M Na2 SO4 Solar 1.6 [108]
electrodeposition
electrophoretic
Ag@g-C3 N4 /ZnS 1.23 vs. RHE 0.3 M KCl Visible 0.1 [109]
deposition
Fluorine-dopedg-
In-situ growth 0.6 vs. Ag/AgCl 0.1 M KOH Visible 0.18 [110]
C3 N4 /TiO2
Ti3+ -TiO2 /O-g-C3 N4 Hydrothermal 0.1 vs. Ag/AgCl 0.1 M Na2 SO4 Visible 0.0034 [111]
Chemical bath
TiO2 @P-C3 N4 /Co3 O4 1.23 vs. RHE 0.5 M Na2 SO4 Visible 1.58 [112]
deposition
Calcinations,
electrostatic
NiFe/N-rGO/g-C3 N4 0.8 vs. Ag/AgCl 0.1 M Na2 SO4 Visible −0.97 [113]
self-assembly, and
hydrothermal

5. Future Perspectives
The experimental evidence revealed that g-C3 N4 -could be used as a photocatalyst and
decent catalyst support material for various metal oxide-based heterostructured electrodes
fabrication [29,114]. However, hybridizing the g-C3 N4 with a second carbon component
could further enhance the overall conductivity of the heterostructured electrodes and the
durability of g-C3 N4 catalysts [40,52,115]. Thus far, experimental investigations indicated
that g-C3 N4 -carbon hybrid catalysts could improve the overall PEC performance.
(i) To further improve the photocatalytic activity and water splitting efficiency, innova-
tive strategies are required to synthesize g-C3 N4 -based heterostructured electrodes
with various hierarchical and porous morphologies [70,91,116].
(ii) Most of the reported heterostructured catalysts have been investigated using g-C3 N4
nanosheet morphologies only. It is worth exploring other morphologies of g-C3 N4
such as nanorods, nanoparticles, nanotubes, porous nanosheets, etc. [61,64].
(iii) The simultaneous modification of g-C3 N4 -based heterostructured electrodes through
one or more of the following methods: (i) the rational design of nanoarrays archi-
tectures, (ii) doping of atoms or molecules, and (iii) loading of various co-catalysts.
These strategies can also offer extraordinary improvement of PEC performance due
to the synergetic effect of the different catalytic mechanisms [63,117].
(iv) Moreover, the theoretical and computational screening investigations must be per-
formed to elucidate the charge transfer mechanism, PEC water splitting efficiency,
stability, and strategies for improving the overall photocatalytic activity of g-C3 N4 -
based catalysts.
(v) In addition, these computational studies can serve as a guide for experimentalists,
especially for selecting the optimal materials and making their hybrid compositions.
Therefore, understanding the effect of materials matrices on water splitting perfor-
mance is needed. It will also help to develop the other requirements of catalysts,
such as stability and cost consumption for the real-time application of the PEC water
splitting process.
(vi) Furthermore, electrolytes used in the PEC water splitting have significant influences
on the overall PEC performance. Besides, it is also essential to maintain the system at
a constant temperature to get accurate PEC measurements. Therefore, it is suggested
to utilize water baths or thermostatic systems during the PEC measurements. In
addition, a light source should also be equipped with infrared cut-off filters to block
the unnecessary heating effect and the evaporation of electrolytes.

6. Conclusions
This review summarized and discussed the recent advances in g-C3 N4 -based binary
and ternary heterostructured electrodes for PEC water splitting. The PEC water splitting
is the most straightforward and promising way to produce solar fuels, considering the
Processes 2021, 9, 1959 21 of 26

safety factor, environmental friendliness, and the abundance of solar energy. The process is
usually carried out at room temperature and the usage of inorganic materials, lending the
system robustness, which is difficult to achieve with organic-based photocatalytic materials.
The g-C3 N4 -based binary and ternary heterostructured electrodes exhibit excellent water
splitting performance and stability due to the synergistic interactions with large surface area
and facile transportation of charge carriers. There are certain drawbacks associated with
PEC water splitting; however, they can be overcome by combining it with the biological
processes that are capable of producing a large quantity of hydrogen. The heterostructured
electrodes made of g-C3 N4 with various binary and ternary semiconductor nanostructured
materials are promising photocatalysts in terms of efficient formation of reactive oxygen
species and lower recombination of electrons and holes. From the results mentioned above,
the ternary g-C3 N4 -based heterostructured electrodes exhibited superior photocurrent
densities with lower Rct value and enlarged visible-light absorption capability when com-
pared to the binary g-C3 N4 -based heterostructured electrodes. This phenomenon could be
attributed to the large surface area, synergistic interfaces among the ternary components
with a quick charge carrier transportation, thus eventually reducing the reunion of charge
carriers. Apart from the experiments discussed here, the g-C3 N4 -based heterostructured
electrodes can also be used in various concentrations of different electrolytes with a wide
range of operating potentials. Experimental studies have revealed that g-C3 N4 -based
heterostructured electrodes could act as efficient photocatalyst support materials for PEC
water splitting. However, several bottlenecks still exist that can hinder the use of g-C3 N4
for the PEC water splitting reactions, which needs further elaborative research on this
fascinating material and the other g-C3 N4 -based heterostructured electrode designs.

Author Contributions: Conceptualization and methodology, writing—original draft preparation,

R.K.; writing—original draft preparation, S.G.P.; writing—editing, T.G.L.; writing—editing, C.R.M.;
writing—editing, D.-Y.L.; resources, J.S.; funding acquisition, writing—review and editing, S.K.B. All
authors have read and agreed to the published version of the manuscript.
Funding: This research was supported by the National Research Foundation of Korea (NRF) funded
by the Korean Government (2020R1A2C1012439; 2021R1F1A1046648 (MSIT)), Republic of Korea.
Conflicts of Interest: The authors declare that they have no known competing financial interests or
personal relationships that could have appeared to influence the work reported in this paper.

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