i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8

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Review Article

Graphitic carbon nitride (g-C3N4) synthesis and

heterostructures, principles, mechanisms, and
recent advances: A critical review

Mohammad Jafar Molaei

Faculty of Chemical and Materials Engineering, Shahrood University of Technology, Shahrood 3619995161, Iran

highlights graphical abstract

g-C3N4 heterostructures are

designed to improve charge carrier
separation.

g-C3N4 heterostructures increase
the life time of electron and hole.

Type II, Z-scheme, and S-scheme
heterostructures show different
charge carrier path.

S-scheme heterojunctions are able
to preserve the powerful photo-
generated electrons and holes.

g-C3N4 heterostructures improve
the photocatalytic performance in
pollutant degradation or H2
production.

article info abstract

Article history: Graphitic carbon nitride (g-C3N4) is a semiconductor polymeric photocatalyst with an
Received 24 March 2023 attractive electronic band structure, a moderate band gap energy, facile synthesis, and
Received in revised form functionalization which can be applied as a photocatalyst in the visible light of the spec-
28 April 2023 trum. The main problem of the g-C3N4 photocatalyst is the recombination of the photo-
Accepted 5 May 2023 generated electron-hole pairs. The photogenerated electrons in the conduction band (CB)
Available online 21 May 2023 tend to return to the valence band (VB) with subsequent recombination which is unfavored
for photocatalysis. It is difficult for a single-component photocatalyst to harvest a large
Keywords: portion of the sunlight spectrum, and simultaneously, possess a suitable spatial charge
Graphitic carbon nitride (g-C3N4) separation and efficient redox ability. Constructing a heterojunction aims to satisfy the
Photocatalyst above three factors in a photocatalyst heterojunction system. Constructing geC3N4ebased
Type II heterostructures heterostructures can promote electron-hole pair separation through the charge transfer
Z-Scheme across the interface of the g-C3N4/semiconductor. In this review, the photocatalysis
mechanism is discussed and several types of g-C3N4/semiconductor heterostructures

E-mail address: m.molaei@shahroodut.ac.ir.

https://doi.org/10.1016/j.ijhydene.2023.05.066
0360-3199/© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8 32709

S-Scheme including type II, Z-scheme, and S-scheme heterostructures are explained. Recent ad-
Hydrogen production vances in different types of geC3N4ebased heterostructures have been addressed. The
synthesis methods for mesoporous, 0D, 1D, and 3D geC3N4 and different modifications on
this photocatalyst are reviewed.
© 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Contents

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32709
Mechanism of heterogeneous photo-catalysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32710
Why heterostructures? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32711
geC3N4ebased heterostructures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32712
Conventional type II heterojunction systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32712
Z-scheme heterojunctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32715
S-scheme heterojunctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32716
Synthesis of g-C3N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32718
Mesoporous g-C3N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32720
2D g-C3N4 nanosheets and thin films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32720
1D g-C3N4 nanotubes/nanorods/nanowires . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32720
0D g-C3N4 quantum dots (QDs) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32720
Modifications to g-C3N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32721
Elemental doping . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32721
Surface engineering of g-C3N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32722
Application of co-catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32722
Loading a single atom in the basal plane . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32722
Defect engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32722
A brief comparison between different g-C3N4 heterojunctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32722
Challenges and future prospective . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32724
Availability of data and materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32724
Declaration of competing interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32724
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32724
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32724

To date, several modifications have been made to increase

Introduction
Fossil energy shortage and environmental pollution are two
global challenges that have risen great concerns. Photo-
catalysis with solar light can address these concerns. Photo-
catalysis by semiconductors can produce fuels such as H2 by
photoelectrochemical (PEC) water splitting and can degrade
environmental pollutants [1]. Among the semiconductors that
have been used for these purposes, graphitic carbon nitride (g-
C3N4) has received great attention in recent years.
The g-C3N4 is a non-toxic, low-cost, and environment-
friendly material that has been used as a photocatalyst in
recent years due to its visible light absorption, tunable
bandgap, and easy synthesis methods. The g-C3N4 can be
synthesized through thermal condensation of nitrogen-rich
precursors, such as melamine, cyanamide, dicyandiamide,
urea, and thiourea. The bandgap of g-C3N4 is x 2.7 eV, the
valence band (VB) maximum is at x1.6 eV and the conduction
band (CB) minimum is at x1.1 eV, vs. normal hydrogen elec-
trode (NHE). This band structure makes the g-C3N4 capable of
absorbing visible light [2].
the photocatalytic activity of g-C3N4. Increasing the number of
active facets has been focused on by changing the morphology
and increasing the surface area. By controlling the growth
process, nanoparticles of g-C3N4 with a large surface area can
be obtained. Doping with elements such as N and B has also
been used to tune the electric properties of g-C3N4 and in-
crease its photocatalytic performance. Among several modi-
fication routes, constructing heterojunctions with other noble
metals and semiconductors is advantageous since can result
in enhancing the charge separation and light-harvesting from
a larger part of the spectrum. The band positions of the het-
erojunction components should be able to accumulate the
space charge at the interfaces of two components to facilitate
the charge carrier separation [3].
Titanium dioxide (TiO2) has dominated the research field in
photocatalysis over the few past decades and has found
several applications in solar cells [4], hydrogen production
from PEC water splitting [5], environmental pollution mitiga-
tion, etc [6,7]. However, the high recombination rate and
inherent wide band gap have limited the wide-scale practical
application of this material. Therefore, numerous research
32710 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8

has been devoted to strategies for charge separation and band

gap engineering of TiO2 to increase its photocatalytic effi-
ciency and increase light-harvesting [8]. Simultaneously, ef-
forts have been devoted to searching for alternative materials
to harvest sunlight and perform photocatalytic activity. The g-
C3N4 is one of the widely applied alternatives. Intensive work
on carbon nitride has arisen since the prediction made by Liu
and Cohen in 1989 that covalent solids formed between ni-
trogen and carbon are superior candidates for reaching ultra-
hard materials [9]. Several types of C3N4 exist including cubic,
pseudocubic, a-, b-, and graphitic which the latter is the most
stable form at ambient conditions [10].
Graphitic carbon nitride (g-C3N4) has a similar skeleton to
graphite with CeN covalent bonds instead of CeC bonds in the
graphite structure. The layers in g-C3N4 are linked to each other
by weak van der Waals forces [11]. The graphitic phase allo-
trope of carbon nitride is the most stable in the ambient envi-
ronment. The basic building blocks of g-C3N4 have been
proposed to be triazine units (C3N3). Tri-s-triazine (heptazine,
C6N7) rings which compared to triazine, are more energetically
favored building blocks of g-C3N4 is the other structural model.
Fig. 1 shows the triazine or tri-s-triazine rings forming g-C3N4
by trigonal nitrogen atoms cross-linking the building blocks
[12].
The large band gap and charge recombination are the
bottlenecks in the development of semiconductors for solar
energy conversion with high efficiency. Thus, the search for a
semiconductor photocatalyst with a suitable band gap resul-
ted in the development of g-C3N4 as a polymeric semi-
conductor that provoked a new wave of excitement in the
research in this field [14]. The g-C3N4 is promising for future
solar-based fuel production and environmental pollution
degradation. The g-C3N4 can also be used in heterojunctions to
construct geC3N4ebased photocatalysts in Fenton-like catal-
ysis for the degradation of pollutants [15]. Furthermore,
compared with the bulk phase, the g-C3N4 with other di-
mensionalities may have a different band gap and also are
easier for some modifications such as interface engineering
and elemental doping [16].
This review aims to give a brief discussion on the mecha-
nism of photocatalysis and clarify why g-C3N4 is preferred to
be used in heterostructure constructions with other suitable Fig. 1 e (a) s-Triazine (top) and tri-s-triazine (bottom) as
semiconductors. Different types of heterostructures that are tectons of possible g-C3N4 allotropes. Adapted with
made with g-C3N4 are introduced and recent advances have permission from Ref. [12] Copyright (2016) The Royal
been discussed. The g-C3N4 can be synthesized in the form of Society of Chemistry. (b) Typical XRD pattern of the g-C3N4
conventional 3D, and also 2D, 1D, and 0D structures. There- synthesized by calcination of urea under air atmosphere.
fore, the review is followed by a discussion of the synthesis Adapted with permission from Ref. [13] Copyright (2016)
methods of g-C3N4 with different dimensionalities. In recent Elsevier Ltd.
years, some other modifications on g-C3N4 have been applied
to increase their photocatalytic efficiency. These approaches
such as elemental doping, surface engineering of g-C3N4, seven stages or four major steps: 1- light harvesting; 2- exci-
application of co-catalyst, and loading a single atom in the tation; 3- charge separation and transfer (also known as stages
basal plane have been addressed. Finally, the challenges and 3, 4, and 5); electrocatalytic reactions (also known as stages 6
prospects of the g-C3N4 heterostructures are explained. and 7) [17,18]. The first stage is strongly dependent on the
morphology and surface structure of the photocatalyst [18,19].
Light harvesting can be enhanced for mesoporous [20] and
Mechanism of heterogeneous photo-catalysis hierarchical microporous morphologies [21] due to multiple
scattering and reflection of light on the surface of the photo-
The mechanism of heterogeneous photo-catalysis is repre- catalyst, while a smooth surface is not suitable for maximum
sented in Fig. 2. The heterogeneous photo-catalysis includes light harvesting. The second stage, excitation, happens when
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
Fig. 2 e The schematic showing the heterogeneous
photocatalysis mechanism. The photocatalysis process
involves 7 steps: (1) harvesting of the light; (2) excitation of
the charges; (3) charge separation and transfer; (4) charge
recombination in the bulk; (5) charge recombination on the
surface; (6) surface reduction reactions; and (7) surface
oxidation reactions. Adapted with permission from
Ref. [18] Copyright (2016) Elsevier B·V.
a photon with an energy equal to or higher than the bandgap
of a semiconductor is received. Upon excitation, an electron
from the valence band (VB) is excited to the conduction band
(CB), leaving a hole in the VB [18]. Compared to other photo-
catalysts such as WO3 [22], BiVO4 [23], and TiO2 [24], the g-C3N4
has a medium band gap of 2.7 eV. Among the aforementioned
photocatalysts, the g-C3N4 has the most negative CB level of
1.3 V vs NHE at pH 7 which has resulted in the development
of this material as a widely used photocatalyst. Several stra-
tegies such as element doping or defect introduction have
been used to further narrow the band gap of g-C3N4 to harvest
more part of the visible light. The third stage, charge separa-
tion and transfer refer to unfavorable charge recombination in
the bulk of the photocatalyst (stage 4) and on the surface
(stage 5) [18]. When there is no driving force, the charge car-
riers take a random pathway in the photocatalyst. Therefore,
there is a great probability for the charge carriers in the pho-
tocatalyst to recombine before any photocatalytic activity.
Only a few electron-hole pairs can be separated and migrate to
the surface of the photocatalyst to participate in the photo-
catalytic reactions, while many of these pairs are consumed
by recombination [25]. The charge separation is needed to
promote charges’ transfer to interface/surface active sites.
This factor can be enhanced by constructing interfacial elec-
tric fields and shortening the diffusion path length for the
charges. A reduction in the recombination rate will result in
an increase in the photocatalyst efficiency. Only the electrons
and holes that have enough energy and are not recombined,
could migrate to the surface and will be trapped by surface
active sites or co-catalysts. These charges can finally partici-
pate in electro-catalytic reduction (stage 6) and oxidation
(stage 7) reactions. The surface reactions happen when the
32711
reduction and oxidation potentials are more positive and
negative than CB and VB levels, respectively. The two factors
that limit the surface photocatalytic performance of reduction
and oxidation reactions are sluggish kinetics and the large
onset overpotential [18]. These obstacles can be conquered by
using a suitable co-catalyst (electrocatalyst) that is loaded on
the photocatalyst. The other role of a co-catalyst is improving
charge separation and photostability [25].
Why heterostructures?
When a semiconductor is in its ground state, has outstanding
chemical stability. However, when the semiconductor is irra-
diated by light, the electrons in the VB will be excited to CB, if
the photon energy is not less than the band gap energy of the
semiconductor. Simultaneously, a hole is produced in the VB of
the semiconductor. If an electric field exists, the electron-hole
pairs can travel to the surface of the semiconductor resulting
in highly active charge carriers on the surface. Therefore, the
generated electrons in CB and holes in VB can act as reductants
and oxidants, respectively. However, the photogenerated
charges still can choose another way; they can recombine on
the surface or interior of the photocatalyst and waste the
reduction or oxidation ability in terms of emitted light or heat.
For preserving the photocatalytic performance of the semi-
conductor, it is necessary to separate the electron-hole pair by
transferring them across the interface/surface to prevent their
recombination. The solution relies on constructing a hetero-
junction by coupling the semiconductor with other substances.
Band bending occurs at the interface by contacting the semi-
conductor with other semiconductors, and an in-built electric
field is generated. Therefore, there will be an increase in the
separation of the electron-hole pairs in a well-designed heter-
ojunction [3].
In recent years, constructing geC3N4ebased hetero-
structures for reaching a more effective photocatalyst has
attracted great attention. Constructing geC3N4ebased heter-
ostructures is aimed to 1- extend the light absorption; 2-
enhance the separation of photogenerated charge carriers, 3-
increase the density of the active site, and 4- increase the
specific surface area. Generally, the most feasible strategy for
enhancing the separation of charge carriers (electron-hole
pairs) is constructing a suitable heterostructure [26,27].
The factors for designing an efficient photocatalyst should
be considered as follow: (1) The photocatalyst should have a
narrow bandgap to be able to absorb a larger part of the solar
spectrum; (2) The VB and CB of the photocatalyst should be
located at energy level more positive and more negative,
respectively. This promotes the electron-hole pair to partici-
pate in the redox reaction more efficiently. (3) The photo-
catalyst with a higher VB and a lower CB level reduces the
probability of electrons returning to VB. It can be promptly
concluded that factor (1) prefers a narrower bandgap for better
light harvesting, while factors (2) and (3) mean that the oppor-
tunity of photogenerated charges for the redox reactions in-
creases by a more positive VB and a more negative CB.
Therefore, factor (1) is on the opposite side factors of (2) and (3)
[28]. It is difficult for a single-component photocatalyst to har-
vest a large portion of the sunlight spectrum, and
32712 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
simultaneously, possess a suitable spatial charge separation
and efficient redox ability. Constructing a heterojunction aims
to satisfy the above three factors in a photocatalyst hetero-
junction system designed by two or more semiconductors
[1,28].
geC3N4ebased heterostructures
Fig. 3 shows different types of geC3N4ebased heterojunctions.
In type II heterojunctions based on g-C3N4 photocatalyst, all
photocatalyst is illuminated by light radiation, and the CB of
photocatalyst II (PCII) receives the electrons from the CB of
photocatalyst I (PCI) due to the potential difference which ex-
ists in this type of heterojunctions. Simultaneously, the holes
in these two semiconductors may move in opposite directions
to electrons. Therefore, the electrons are assembled in the CB
of photocatalyst II and holes are assembled in the VB of pho-
tocatalyst I to induce a reduction reaction and oxidation re-
action, respectively [28]. These charge transfers improve the
spatial charge separation and reduce the probability of
recombination which leads to improved oxidation and reduc-
tion reactions [29,30]. In Z-scheme heterojunction the charge
transfer process is different. The charge-carrier migration
pathway in a Z-scheme system resembles the letter “Z” in
English. Generally, the photogenerated electrons in a semi-
conductor with a lower reduction ability, recombine with the
photogenerated holes in a semiconductor with a lower oxida-
tion ability [27]. Both photocatalysts can generate electrons
and holes in this type of heterojunction. The transfer path for
the photo-generated electrons is from CB of PC II to VB of PCI
through the heterojunction or a special electron mediator to
couple with the holes of PC I. Therefore, the photo-generated
electron and holes are retained in the CB of PC I and the VB of
Fig. 3 e (a) Different Photocatalytic mechanisms and (b) electron and hole transfer paths in type-I, type-II, and Z-scheme
heterojunction. Adapted with permission from Ref. [28] Copyright (2020) Elsevier B·V.
PC II, respectively. The photo-generated electrons and holes
have reducibility and oxidability, respectively [28].
Conventional type II heterojunction systems
The main problem in photocatalysts is the recombination of
the photogenerated electron-hole pairs. The photogenerated
electrons in the CB tend to return to VB with subsequent
recombination which is unfavored for a photocatalyst [31].
However, when a semiconductor with a suitable band struc-
ture lays in intimate contact with the g-C3N4, the charge
transfer across the interface of g-C3N4/semiconductor will
promote the electron-hole pair separation. g-C3N4 can be used
as a photocatalyst due to its sufficiently negative CB position
[26].
For type II heterojunction, upward or downward band
bending is due to the difference of chemical potential in the
component semiconductors which controls the charge carrier
migration in the opposite direction. Through this hetero-
junction, charge separation is achieved and the lifetime of the
electron and hole will be prolonged [32].
Fig. 4 shows that conventional geC3N4ebased type II het-
erojunction is an effective system for spatial separation of the
electron-hole pairs. The most important factor that should be
considered in constructing such a heterojunction, is the band
structure of the adjacent semiconductor. Fig. 4a shows a
heterojunction of a semiconductor with a more negative CB
level in intimate contact with g-C3N4 which in this case, after
electron-hole pair separation, the electron can retain on the
CB of the g-C3N4. But these kinds of semiconductors (with a CB
more negative than that of g-C3N4) are uncommon. Generally,
the heterostructures shown in Fig. 4b are easier to be con-
structed [26].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8 32713

enhanced photocatalytic activity. The Nb2O5 has been used in a

Fig. 4 e Schematic illustration of conventional type II
geC3N4ebased heterostructure charge transfer; (a) with
more negative CB level and (b) with more positive VB level.
Adapted with permission from Ref. [26] Copyright (2017)
WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Several type II heterojunctions based on g-C3N4 have been
developed in recent years. Type II ZnSe/g-C3N4 heterojunction
was synthesized by ultrasonication method and evaluated for
PEC water splitting. Linear sweep voltammetry of (0.05%
ZnSe)/g-C3N4 revealed a six-fold higher photocurrent density
of 500 mA than g-C3N4. Since there is a suitable potential
difference in the designed heterojunction, the photoexcited
electrons in the CB of ZnSe will be transferred to the CB of g-
C3N4 and then to the counter electrode through an external
circuit. Then these electrons can impart in the reduction of
water and H2 generation [33]. Type II Cu2O/g-C3N4 hybrids also
showed improved photocatalytic activity toward hydrogen
generation compared to pure bulk g-C3N4. The hydrogen
evolution rate can reach 4 times higher than that of pure g-
C3N4 which has been attributed to the better separation of the
charge carriers at the interface between g-C3N4 and Cu2O [34].
Niobium pentoxide (Nb2O5) is a semiconductor with a band
gap of z3.2 eV and is a promising photocatalyst due to its good
photostability. This oxide has been used in conjugate with
several semiconductors to result in heterojunction with
type-II heterojunction with g-C3N4 for converting the sunlight
to H2 through photocatalytic water splitting. By using 5 wt%
Nb2O5 in the heterojunction, the H2 evolution rate reaches
more than 4-fold to that of pure g-C3N4. The synthesized Nb2O5
and g-C3N4 have intimate contact which can boost the effi-
ciency of the heterojunction (Fig. 5) [35]. The construction of
Nb2O5/g-C3N4 heterojunction resulted in significant band
shifting toward lower hydrogen evolution reaction (HER) po-
tential. This design was able to show several folds of increased
photocurrent response from PEC water splitting [36].
The photocatalytic activity of g-C3N4 is severely dependent
on the crystallinity. It has been reported that poor crystallinity
will decrease the photocatalytic performance of pristine g-
C3N4. Therefore, increasing the crystallinity of g-C3N4 can
improve its photocatalytic performance [37]. Two-
dimensional (2D) high-crystalline g-C3N4 nanosheets can
reduce the rate of charge recombination due to their lower
defect density and hence, improving carrier transport effi-
ciency. The structure and morphology of the photocatalyst are
key factors that can determine the surface area and utilization
of visible light of the photocatalyst [38]. For example, 2D high
crystalline g-C3N4 (HCCN) nanosheets were used in a hetero-
structure with three-dimensional (3D) yolk-shell ZnFe2O4
(ZFO). It was found that light harvesting and charge separation
efficiency are greatly improved by the formation of hetero-
junction. The degradation rate of tetracycline by the hetero-
junction reached 85%, and the degradation rate constant
enhanced 3.8 and 4.9 times higher compared to HCCN and
ZFO, respectively (Fig. 6) [38].
TiO2 has received great attention among other photo-
catalysts such as Bi2WO6, V2O5, WO3, ZnS, ZnO, etc, due to its
low cost, environmental friendliness, non-toxic nature, and
high stability. However, due to its wide bandgap, TiO2 is only
active in the ultraviolet region of the spectrum and covers
only 4% of the solar cell radiation. Therefore, different
methods have been applied to increase the photocatalytic
activity of TiO2. Among several methods that have been used

Fig. 5 e High-resolution TEM image of the synthesized Nb2O5/g-C3N4 heterojunction, (b) Comparison of H2 evolution rate for
heterojunctions with different Nb2O5 content: NOCN-x, where x ¼ 2.5, 5 or 7.5 for g-C3N4 heterojunction with 2.5, 5, and
7.5 wt% Nb2O5, respectively. (c) The schematic illustrates the mechanism of charge carrier separation and transfer in the
Nb2O5/g-C3N4 type-II heterojunctions under visible (left) and simulated solar light (right). Adapted with permission from
Ref. [35] Copyright (2021) Elsevier Inc.
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Fig. 6 e SEM images for (a) ZnFe2O4 and (b) 20% g-C3N4/ZnFe2O4. (c, d) TEM, (e) HRTEM images for 20% g-C3N4/ZnFe2O4. (f)
schematic that shows the mechanism of photocatalytic reaction for the degradation of tetracycline over 2D/3D HCCN/ZFO (g-
C3N4/ZnFe2O4) heterojunction. (g) tetracycline degradation curves. (h) comparison of tetracycline degradation rates by bulk
g-C3N4 (BCN), 20% BCN/ZFO, HCCN (2D g-C3N4), and 20% HCCN/ZFO. Adapted with permission from Ref. [38] Copyright (2022)
Elsevier Ltd.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8 32715

to improve the charge separation of TiO2, constructing het-
erojunction with g-C3N4 is a solution for the reduction of the
recombination rate of charge carriers. For example, g-C3N4
was coupled with TiO2 by a hydrothermal method to result in
a type II heterojunction. The heterojunction was used for
hydrogen production through a photocatalytic process. The
heterojunction with a high TiO2 content achieved a produc-
a shuttle redox mediator (electron acceptor/donor pair). The
shuttle redox mediator facilitates electron transportation
from the CB of photocatalyst I to the VB of photocatalyst II
(Fig. 7aec). The limitation of the traditional Z scheme photo-
catalysts is the reversibility of the redox mediator. Further-
more, the redox mediator is restricted to liquid-phase
applications only [41e43]. Example of redox mediator is IO
3 /I


tion rate of 1041 mmol g1.h [39]. 3þ 2þ

Z-scheme heterojunctions
The term ‘Z Scheme’ is a name that is adopted from the nat-
ural photosynthesis process. The traditional Z scheme was
initially explained by Bard [40] in which, a liquid phase Z
scheme was designed with two semiconductors attached with
and Fe /Fe [44,45]. The lack of direct contact between two
semiconductors in the aqueous condition leads to the de-
pendency of this type of heterostructure on the redox couples.
The redox mediators should have sufficient cyclability under a
given reaction condition, good light transparency, and suit-
able potentials. They can act as the electron donor and
acceptor and consume the photoexcited charge carriers of
electrons in the CB of one semiconductor and holes of the VB
of the other semiconductor, respectively [46]. However, in

Fig. 7 e Schematic showing (a) traditional, (b) all solid-state, and (c) direct Z scheme photocatalyst. (d) several
semiconductors that have been applied in the Z scheme geC3N4ebased photocatalyst with the illustration of their band
structure. Adapted with permission from Ref. [41] Copyright (2019) The Korean Society of Industrial and Engineering
Chemistry. Published by Elsevier B·V.
32716 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
2006, a new type of Z scheme photocatalyst was introduced in
which a noble metal nanoparticle was used as an electron
mediator in conjugate with two semiconductors [46,47]. Other
conductive materials such as graphene and carbon nanotube
have also been applied as the electron mediator instead of the
noble metal nanoparticle [48,49]. The application of noble
metal nanoparticles can prevent a backward reaction in the
traditional Z scheme photocatalysts. However, such a design
restricts the wide application of this type of photocatalyst [41].
For the first time, a direct Z scheme photocatalyst of g-C3N4
was designed by the application of g-C3N4 in a heterojunction
with TiO2. Direct Z scheme photocatalysts have the advantage
of direct contact between the photocatalysts and reduce the
photocatalyst synthesis cost [50].
When designing a Z scheme photocatalyst, it should be
considered that the holes with a higher oxidation potential
and the electrons with a higher reduction potential are pre-
served. This criterion can be satisfied by combining an
oxidation photocatalyst with a reduction photocatalyst. The
oxidation photocatalysts show a high oxidation ability and
they have higher oxidation potential. Similarly, reduction
photocatalysts show strong reduction ability and they have
high CB potential. The g-C3N4 is a reduction photocatalyst.
Therefore, to increase the efficiency, this photocatalyst should
be combined with an oxidation photocatalyst. The band
structures of several photocatalysts that have been used in
conjugate with g-C3N4 are illustrated in Fig. 7d. The Z scheme
photocatalyst can make spatial separation of oxidation and
reduction locations. Furthermore, this type of photocatalyst
facilitates the simultaneous preservation of the strong
oxidation potential and reduction potential [41].
Ball milling is a facile technique that can be used for the
production of heterojunction photocatalysts. Ball milling is
cost-effective and can introduce defects into the structure of
the milled powder particles. Z-scheme heterojunction CeO2/g-
C3N4 nanocomposites have been synthesized by the ball
milling method of the initial powders. It was observed that the
nanocomposite of CeO2/g-C3N4 shows better charge separa-
tion, stronger UV light response, higher photocurrent density,
greater photodegradation potential, and faster electron
transfer which can improve the photocatalytic activity of the
nanocomposite compared to pristine g-C3N4. The nano-
composite of 70% CeO2/g-C3N4 exhibited the highest photo-
catalytic activity in the removal rate of the methylene blue
(MB) under UV light irradiation. The removal rate for MB was
found to be 90.1% compared to pure g-C3N4 and CeO2 with
removal rates of 45.7% and 6.2%, respectively [51].
The defects strongly affect the photocatalytic performance
of the Z-scheme heterojunctions. The combination of defect
engineering and heterojunction construction might minify
the bandgap width and improve the visible light absorption of
the heterojunctions. Among the low-dimension nano-
composites (0D, 1D, and 2D), the, 2D/2D stacked hetero-
junctions in Z-scheme systems have a high photocatalytic
performance. 2D/2D Z-scheme g-C3N4/hexagonal boron
nitride (hBN) nanosheets were constructed while single car-
bon atoms were doped on the hBN constituent. In another
construction, a specific boron atom was substituted with
carbon impurity in the hBN/g-C3N4 bilayer. While impurity
engineering is successful in increasing the photocatalytic
performance of this heterostructure, vacancy-engineered can
also tune the electronic structure and band gap accordingly
[52].
The Z-scheme heterojunctions can be used for increasing
the photocatalytic performance of sulfate radical-mediated
photocatalysis technology of g-C3N4. Sulfate radical-
mediated photocatalysis technology is an approach that can
be used for the activation of peroxymonosulfate (PMS) for
photocatalytic performance. The PMS can be activated by a
catalyst and visible light which results in the generation of
reactive species (hydroxyl radicals (
OH) and sulfate radicals,
SO

4 ). The PMS can be activated by a catalyst and visible light
and generates reactive species of hydroxyl radicals and sulfate
radicals. The PMS activation efficiency of g-C3N4 is limited due
to the high recombination rate of charge carriers. Therefore,
Co3O4 has been used in a Z-scheme heterojunction with g-
C3N4 to overcome this shortage in photocatalysis. In the 10%
Co3O4/g-C3N4/Vis/PMS system, the charge carriers transfer
between g-C3N4 and Co3O4 followed by a Z-scheme type.
When the heterojunction is irradiated by light, the electrons of
VB of Co3O4 and (or) g-C3N4 can be excited. The excited elec-
trons are transferred to their CB. The electrons in the CB of
Co3O4 are transferred to the VB of g-C3N4. The produced holes
in the VB of Co3O4 generate
OH by reaction with OH. The
remained electrons in the CB of g-C3N4 will also produce
O2
by reaction with O2 [53].
S-scheme heterojunctions
The photocatalysts can be classified as oxidation photo-
catalysts (OP) and reduction photocatalysts (RP), depending on
their band structures. Ops are mainly used in environmental
degradation. In OPs, photogenerated electrons are fruitless,
while photogenerated holes are the contributive factors
(Fig. 8a). In comparison, RPs, which have the characteristic of a
high CB, are mainly used for the production of solar fuels. In
RPs, photogenerated holes are useless and should be removed
by sacrificial agents, while photogenerated electrons are
effective. The S-scheme heterojunction is composed of OP and
RP with staggered band structures. The S-scheme band
structure is similar to type-II heterojunction but the charge-
transfer route is different (Fig. 8b and c). In a typical type-II
heterojunction, photogenerated electrons and holes accu-
mulation occurs on the CB of OP and VB of RP, respectively.
This will lead to a weak redox ability. However, in an S-
scheme heterojunction photocatalyst, the photogenerated
electrons and holes that are powerful are accumulated in the
CB of RP and VB of OP, respectively. In this type of hetero-
junction, recombination occurs for the pointless photo-
generated charge carriers. This will lead to a strong redox
potential [54]. The charge transfer in S-Scheme hetero-
junctions can be explained in this order.
(1) The VB and CB of RP are at higher positions and the
work function is smaller compared to OP (Fig. 8d). The
contact of these two semiconductors causes to RP
electrons diffuse to OP which creates a layer depleted of
electrons and a layer with accumulated electrons near
the interface of the contact RP and OP, respectively. The
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Fig. 8 e (a) Band structure of some of the photocatalysts compared to g-C3N4. Charge transfer comparison between (b) Type-
II and (c) S-Scheme heterojunctions. (def) S-Scheme heterojunction with staggered band configuration charge-transfer
processes: (d) before and (e) after contact, (f) S-scheme mode photogenerated charge carrier transfer process. Adapted with
permission from Ref. [54] Copyright (2020) Elsevier Inc.

RP is positively charged and OP is negatively charged. CB of OP and holes in the VB of RP to be recombined at

Concurrently, an internal electric will be formed with
the direction from RP to OP (Fig. 8e). This created in-
ternal electric field results in the acceleration of the
transfer of the photogenerated electrons from OP to RP,
instead of the other way round (see Fig. 8f).
(2) By making intimate contact between RP and OP, Fermi
energy should be aligned to the same level. Therefore,
there would be a downward and upward shift in the
Fermi levels of RP and OP, respectively. The band
bending promotes the photogenerated electrons in the
the interface, similar to the flowing of water downhill.
(3) Due to the Coulombic attraction, the holes in the VB of
RP and electrons in the CB of OP are inclined to
recombine at the interface. On the other hand,
Coulombic attraction, band bending, and the internal
electric field are the three main factors that act as the
driving forces for the recombination of holes in the VB
of RP and electrons in the CB of OP. Therefore, the
powerful photogenerated electrons in the CB of RP and
the holes in the VB of OP participate in the
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photocatalytic reactions, while useless charge carriers
will be recombined and eliminated [54].
A molecular-level and dynamic view of the S-scheme het-
erojunction was provided by using time-resolved photo-
luminescence spectroscopy and ultrafast transient absorption
spectroscopy for inorganic/organic TiO2/polydopamine (PDA)
heterojunction. It was found that the charge transfer in S-
scheme heterojunction happens faster than in the recombi-
nation process. This will lead to an effective separation of
charge carriers. This composite exhibits higher photocatalytic
activity in H2O2-production. The band structure and electron
transfer mechanism of this S-scheme heterostructure are
illustrated in Fig. 9. When PDA and TiO2 come into contact, free
electrons are migrated from the PDA side to the TiO2 side due to
the higher Fermi level of the PDA. The charge transfer con-
tinues until matching the Fermi levels. Therefore electron
depletion on the PDA side and electron accumulation on the
TiO2 side occurs. The internal electric field will be generated
pointing from the PDA to the TiO2 side. The band bending also
occurs at the interface. When the heterostructure is irradiated,
electron-hole pairs are photogenerated both on PDA and TiO2.
Under the generated internal electric field, the electrons in the
CB of TiO2 are transferred to the HOMO of PDA within an ul-
trashort period (~5 ps) and these electrons then, are photoex-
cited to the LUMO of PDA, while the holes stay in the VB of TiO2.
Simultaneously, the recombination process which occurs in a
longer period (~10 ns) is suppressed. This type of hetero-
junction provides stronger redox potentials and effective
charge separation [55]. The s-scheme heterostructure of g-
C3N4/PDA was also constructed by in situ self-polymerization
and was used for H2O2 production. The composite showed a
photocatalytic production rate of 2 and 11 times higher than
that of pure g-C3N4 and PDA, respectively [56].
The electron transfer pathway in the S-scheme hetero-
structures can be studied with the help of in situ irradiated X-
ray photoelectron spectroscopy (ISIXPS). In this technique, X-
rays and UVevis light irradiate the sample surface, simulta-
neously. X-ray excites the electrons from the inner-shell
electron layer of the atom, while UVevis irradiation excites
the electrons of valence to the CB. Under photoexcitation, the
changes in elemental binding energy (Eb) and electron density
of the heterostructure are measured. The change in electron
density can be sensed by the change in the Eb of an element.
The electron density of RP decreases after contact and the Eb
of constituent elements in RP increase. For OP the electron
density increases after contact in this type of heterostructure
and the elemental Eb decreases. ISIXPS can also detect the
transfer direction of the charge carriers since under irradia-
tion, the photogenerated electrons in the CB of OP are trans-
ferred to the VB of RP, resulting in an increased electron
density in RP and accordingly, a reduced electron density in
OP [57].
In recent years, different kinds of g-C3N4 heterojunctions
have been constructed for photocatalytic reactions. Type II, Z-
scheme, and S-scheme heterojunctions have been used for
PEC, hydrogen production, and environmental applications.
Table 1 represents different g-C3N4 heterojunctions and their
photocatalytic performance.
Synthesis of g-C3N4
Reactive oxygen-free and nitrogen-rich compounds contain-
ing pre-bonded CeN core structures are the common pre-
cursors for the synthesis of g-C3N4. Such materials (e.g.
heptazine and triazine derivatives) are unstable and/or highly
explosive. The synthesis of g-C3N4 with defects is preferred
when it is going to be used in catalysis. For the production of
defective polymeric species, the condensation pathways from
cyanamide to dicyandiamide, melamine, and all other C/N
materials can be applied. The cyanamide at ca. 550  C in the
air or inert atmosphere is transformed to g-C3N4 [78]. The g-

Fig. 9 e Schematic illustration of (a) the band structures of PDA and TiO2, (b) the formation of internal electric field and
electron transfer in the heterojunction after contact, (c) The charge transfer and the mechanism of the S-Scheme
heterostructure after light irradiation. The time scales for recombination, interfacial transfer, and electron trapping are
labeled. Adapted with permission from Ref. [55] Copyright 2022 American Chemical Society.
Table 1 e Different g-C3N4 heterojunctions and their photocatalytic performance.
Photocatalyst Type of the Photocatalytic application Photocatalyst performance Illumination Reference
heterojunction
Co3O4eBiVO4/g-C3N4 Z-Scheme degradation of KN-R dye the removal rate of 99.6% in 30 min xenon lamp [58]
Co3O4/g-C3N4 Z-Scheme hydrogen evolution the evolution rate of 50 mmol h1g1 300 Wxenon lamps [59]
BiO1-XBr/g-C3N4 Z-Scheme degradation of RhB about 100% degradation in 25 min xenon lamp [60]

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
Ag-bridged Bi5FeTi3O15/g-C3N4 Z-Scheme degradation of tetracycline 48 and 60% in 40 min for visible visible light ((l > 420 nm) and [61]
light and simulated solar light, 300 W xenon lamp
respectively
LaNiO3/g-C3N4 Z-Scheme photocatalytic water splitting yield of up to 300 W xenon lamp [62]
3392.50 mmol g1 within 5 h and a 250 < l < 380 nm
H2 evolution rate of
678.5 mmol h1 g1
Ag/AgVO3/carbon-rich g-C3N4 Z-Scheme degradation of sulfamethiadiazole degradation of 98.2% in 30 min xenon lamp with a 420 nm [63]
cutoff filter
CoS/g-C3N4/NiS Z-Scheme hydrogen evolution 1.93 mmol g1 h1 300 W xenon arc lamp [64]
AgIO4-g-C3N4 Z-Scheme hydrogen production and hydrogen production rate of 350 W xenon lamp [65]
photodegradation of fluorescein dye 23 mmol h1 g1 and 98% removal
of fluorescein dye
K4Nb6O17/g-C3N4 Z-Scheme H2generation and RhB degradation H2 generation of ~16.91 mmol h1 300 W xenon arc lamp [66]
(l > 420 nm)
g-C3N4/NiAl-LDH type-II CO2 photocatalytic reduction CO production rate of 300 W xenon lamp [67]
28.83 mmol g1 h1
BaTiO3/g-C3N4 type II degradation of methylene blue (MB) dye 91% in 90 min sunlight irradiation [68]
Nb3O7F/g-C3N4 type II hydrogen evolution 427.2 mmol h1 g1 300 W xenon lamp [69]
BiOBr-g-C3N4 type II removal of RhB 1.51 mmol (gphotocatalyst min)1 300 W xenon lamp equipped [70]
with a cutoff filter (l  420 nm)
2D/2D ZnIN2S4/g-C3N4 type II H2O2generation and consumption H2O2 yield of 4.27 mmol g1 different wavelength filters [71]
(400, 420, 450, and 500 nm) on
axenon lamp
1D b-keto-enamine-based covalent type II hydrogen evolution 12.8 mmol g1 h1 300 W xenon lamp [72]
organic framework (COF)/2D g-C3N4
CsxWO3/g-C3N4 type II CO2photocatalytic reduction 6.79 mmol g1 h1 full spectrum light irradiation [73]
MOFs-derived C-IN2O3/g-C3N4 type II CO2photocatalytic reduction CO (153.42 mmol g1 h1) and UV lamp irradiation [74]
CH4 (110.31 mmol g1 h1)
2D/2D Co3(PO4)2/g-C3N4 type II photocatalytic water splitting H2 and O2 evolution rates of 375.6 xenon lampequipped with a [75]
and 177.4 mmol g1 h1, long pass wavelength filter of
respectively l > 400 nm
MoS2/g-C3N4 S-scheme degradation of Rhodamine B (RhB) 90% in 1 h 100 W lamp with a filter cutting [76]
off UV rays (200e400 nm)
2D/2D BiOBr/g-C3N4 S-scheme degradation of RhB 99% of RhB (10 mg L1, 100 mL) 300 W xenon arc lamp equipped [77]
within 30 min with a 400 nm cut-off filter

32719
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C3N4 can be produced with different dimensions and mor-
phologies which are discussed in the following sections.
Mesoporous g-C3N4
Mesoporous photocatalytic materials including macroporous
structures could exhibit better photocatalytic activity since
they can transport guest species to framework-binding sites.
Furthermore, these types of structures have a higher specific
surface area, offering more active sites for photocatalytic re-
actions. Mesoporous g-C3N4 can be synthesized by a meso-
porous template or without a template. Macro/mesoporous g-
C3N4/TiO2 heterojunction has been synthesized by calcination
a mixture of macro/mesoporous TiO2 powders and melamine
[79]. Mesoporous g-C3N4 can also be synthesized by casting/
replication of SiO2 spheres or mesoporous SiO2 objects. For
this purpose, cyanamide and SiO2 sol are mixed in an aqueous
solution in an oil bath to remove the water. Then, the resul-
tant product is transferred to a crucible (with a lid) to be
heated at 550C for about 4 h. Upon heating, the precursor is
condensed into polymeric carbon nitride. Mesoporous g-C3N4
can be obtained by using ammonia hydrogen difluoride for
dissolving the SiO2 template [12]. Mesoporous g-C3N4 has been
used in different photocatalysts including perylene tetra-
carboxylic diimide covalently bonded with mesoporous g-
C3N4 [80], direct Z-scheme hollow mesoporous g-C3N4/
Ag2CrO4 photocatalysis [81], ultrathin mesoporous g-C3N4/
NH2-MIL-101 (Fe) octahedron heterojunction [82], mesoporous
g-C3N4/MXene (Ti3C2Tx) heterojunction [83], Ag-loaded mes-
oporous g-C3N4 [84], Carbon dots incorporated in hierarchical
macro/mesoporous g-C3N4/TiO2 as an all-solid-state Z-
scheme heterojunction [85], mesoporous g-C3N4/ZnO nano-
sheets photocatalyst [86], ultrathin MoS2 as a cocatalyst on
mesoporous g-C3N4 [87], and mesoporous g-C3N4/ZneTi LDH
laminated van der Waals heterojunction nanosheets [88].
2D g-C3N4 nanosheets and thin films
2D materials have found several applications in electronics
[89], biomedical [90], solar cells [91], removal of pollutants
from water [92], etc. Low-dimensional heterostructure and
photocatalyst materials are essential research topics in the
field of artificial photocatalysis. Low-dimensional geC3N4-
ebased heterostructures have been developed with the aims
of improved migration of charge carriers and charge separa-
tion, harvesting of visible-light range, and increased adsorp-
tion sites on the surface of the photocatalyst that could result
in enhanced photocatalytic reactions [32]. Compared to bulk
g-C3N4, the 2D g-C3N4 nanosheets have shorter bulk diffusion
lengths and higher specific surface area which means they
have a higher number of active sites for photocatalytic re-
actions [93]. Layered g-C3N4 possibly can be achieved since the
g-C3N4 structure is set up by a graphite-like layered structure.
Similarly to graphite, the in-plane bonding for g-C3N4 is strong
CeN covalent bonding (compared to CeC bonding in graphite)
and weak van der Waals interactions exist across the layers.
The ultrathin g-C3N4 nanosheets can be well dispersed due to
the strong repulsion caused by surface charges [12]. Chemical
exfoliation in the presence of concentrated sulphuric acid as
the solvent is one of the facile methods for the preparation of
single atomic 2D g-C3N4 nanosheets. Through this process, by
the strong acid, the planar cohesion of g-C3N4 will be broken
by destroying the NH/NH2 hydrogen bonds between strands of
polymeric melon units [93]. g-C3N4 nanosheets have been
used in different photocatalysts including flower-like MoS2/g-
C3N4 nanosheet heterojunctions [94], metallic Ni3C@ Ni core-
shell cocatalysts over g-C3N4 nanosheets [95], Ti3C2 MXene
embellished g-C3N4 nanosheets [96], biowaste derived hy-
droxyapatite embedded on two-dimensional gC3N4 nano-
sheets [97], NieCu bimetallic co-catalyst g-C3N4 nanosheets
[98], 2D/2D Ti3C2 MXene/g-C3N4 nanosheets [99], MoO3 nano-
paticles/g-C3N4 nanosheets 0D/2D heterojunction [100], and
CuO and ZnO co-anchored on g-C3N4 nanosheets [101].
1D g-C3N4 nanotubes/nanorods/nanowires
The g-C3N4 that has grown in one dimension is ideal for carrier
transport which is advantageous in the photocatalytic per-
formance. Extensive works have been devoted to the synthe-
sis and modification of one-dimensional g-C3N4
nanostructures, especially in heterojunctions. The trans-
formation of g-C3N4 nanoplates to nanorods has increased the
intensity of the photocurrent response and the photocatalytic
activity of g-C3N4 by 2.0 and 1.5 times, respectively [2]. In an
attempt, rod-like g-C3N4 nanostructure was synthesized by
heating melamine at 430  C for 4 h to synthesize melem. The
melem was dispersed in deionized water followed by soni-
cation. The resultant melem hydrate was washed with
ethanol and dried. Then the product was obtained by calci-
nation of the melem hydrate at 550  C [102]. 1D g-C3N4 nano-
structures have been used in different photocatalysts
including S/Cd co-doped g-C3N4 nanorods [103], NiFe2O4
deposited S-doped g-C3N4 nanorod [104], highly ordered TiO2
nanotube arrays embedded with g-C3N4 nanorods [105], and
modified g-C3N4 nanorod/Ag3PO4 nanocomposites [106].
0D g-C3N4 quantum dots (QDs)
In recent years emerging kinds of quantum dots (QDs) such as
carbon quantum dots have been widely used in photocatalytic
reactions [107e114]. One of the possible strategies for
increasing the photocatalytic performance of g-C3N4 is the
synthesis of 0D QDs from 2D nanosheets. The g-C3N4 QDs
possess a higher number of active sites for photocatalytic re-
actions. They can be synthesized from g-C3N4 nanosheets by a
hydrothermal method. The g-C3N4 QDs have an absorption
range from visible to near-infrared region of the spectrum and
hence, can harvest a larger part of the light [115]. As an
example, fluorescent g-C3N4 QDs have been synthesized from
sodium citrate and urea by a solid-state method. In this
experiment, urea and sodium citrate (molar ratio of 6:1) have
been treated hydrothermally at 180  C. The quantum dots can
be extracted from the resultant yellowish solution through
dialysis [116]. QDs of g-C3N4 have been used in different
photocatalysts including Z-scheme g-C3N4 QDs/TiO2 nano-
flakes [117], Ag and g-C3N4 QDs co-decorated 3D hierarchical
Fe3O4 hollow microspheres [118], g-C3N4 QDs on 1D branched
TiO2 loaded with plasmonic Au nanoparticles [119], 0D/1D Z-
scheme g-C3N4 QDs/WO3 composite [120], and B-doped g-C3N4
QDs-modified Ni(OH)2 nanoflowers [121].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8 32721

Modifications to g-C3N4 Elemental doping

Pristine g-C3N4 has high charge-carrier recombination and
limited active sites which are not preferred for photocatalytic
applications. In the past decade, several strategies have been
developed to make modifications to g-C3N4 to increase its ef-
ficiency for photocatalytic applications. Five commonly used
strategies are single-atom modification, surface engineering,
crystalline manipulation, copolymerization, and elemental
doping [122].
The incorporation of metal or nonmetal heteroatoms into the
g-C3N4 structure can alter the physicochemical, electronic,
and absorption properties. Furthermore, the CB and VB of g-
C3N4 can be adjusted by molecular orbital coupling and
elemental orbital doping [122].
Fig. 10a shows by doping non-metallic elements, the band
structure of g-C3N4 changes. The majority of non-metallic
element-doped g-CN, compared to pristine g-C3N4, has a
narrower band gap. This will in turn give them the potential to

Fig. 10 e (a) Band structure of non-metallic elements doped-g-C3N4, (b) Band structure of metallic elements doped-g-C3N4.
Adapted with permission from Ref. [123] Copyright (2021) Royal Society of Chemistry.
32722 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
absorb more light and hence, have better photocatalytic ac-
tivity. The observed changes in the band gap of the non-
metallic elements-doped g-C3N4 can be attributed to (1) the
introduction of defects due to the doping of elements during
the synthesis process which increases the optical absorption
and (2) electronic integration due to doping that alters the
bandgap. The electronegativity difference among N, C, and
doped elements has resulted in a wide range for the CB and VB
of non-metallic element-doped g-CN materials. This variation
of CB and VB, in some cases, can result in a wider band gap. In
the case of metallic element-doped g-C3N4 materials, as
shown in Fig. 10b, the CB and VB positions are various and
these materials possess narrower band gaps compared to
pristine g-C3N4. The charge-transfer transition between the
CB or VB of the g-C3N4 and the electrons of the doped metallic
element leads to a redshift of absorption edge and a narrower
band gap. Furthermore, when metallic elements are doped
into the pristine g-C3N4, a midgap state can be produced in the
bandgap that can hold the photo-excited electrons from VB.
This midgap state can enhance the transfer process of pho-
togenerated electrons [123].
Surface engineering of g-C3N4
The adsorption sites of the surface-engineered g-C3N4 can be
increased, carrier recombination can be inhibited, and the
absorption of the protons can be increased [122]. For better
photocatalytic activity, a decrease in the recombination of
photo-generated charge and an increase in visible light ab-
sorption are essential. However, under light irradiation, most
geC3N4ebased photocatalysts have low catalytic activity,
when co-catalysts are not used [124]. For the photocatalytic
process, a charge should be generated by light absorption
followed by charge separation and migration along with sur-
face redox reaction. The light absorption and charge separa-
tion/migration are the fast processes falling within ps to ns
and ns to ms, respectively. However, the surface redox reac-
tion is the slowest process falling in the range of ms and s.
Therefore, the redox reaction is a rate-determine step in the
photoelectrochemical and photocatalytic reactions [125].
Catalytic kinetics on the surface of g-C3N4 is sluggish since
pristine g-C3N4 is of high overpotential to carry these reactions
on its surface. Therefore, it is necessary to reduce catalytic
reaction overpotential which could be carried on the surface
of g-C3N4 with a fixed energy level of photogenerated charges
[124].
Application of co-catalyst
Surface engineering by introducing co-catalysts has been
applied to enhance photocatalytic water splitting [126]. In the
case of g-C3N4, an oxidation co-catalyst is effective since g-
C3N4 has low oxidation ability and suffers from self-
decomposition due to nitrogen-containing photocatalysts
and inferior valence band potential [127]. In other words, by
constructing a catalytic active site that promotes O2 evolution
on the g-C3N4 surface, the oxidative decomposition of g-C3N4
accompanied by N2 evolution may be hindered. RuO2 which is
a good oxidation catalyst for O2 evolution was introduced on
the surface of g-C3N4. By loading the g-C3N4 with RuO2, the
photocatalytic activity increases due to an increase in the
active sites for O2 evolution. Furthermore, the N2 evolution
due to the decomposition of g-C3N4 decreased considerably.
The RuO2 nanoparticles seem to capture photogenerated
holes that are migrated from g-C3N4 [128]. Cobalt-
incorporated sulfur-doped g-C3N4 has been used in a hetero-
junction with bismuth oxychloride (Co/S-gC3N4/BiOCl) by a
hydrothermal method. It was observed that the PEC water-
splitting activity was enhanced by constructing an interface
between a cocatalyst and the photocatalyst. The enhanced
PEC activity was attributed to improving electron and hole
separation [129].
Loading a single atom in the basal plane
For semiconductor photocatalysts, noble metals such as Pt
have been loaded on their surface to enhance photocatalytic
activity. The reason that Pt increases the photocatalytic effi-
ciency lies behind its lowest overpotential for hydrogen evo-
lution. The hydrogen adsorption/desorption free energy of
active atoms can determine the overpotential for hydrogen
evolution in photocatalytic processes. Rather than simple
deposition of noble metal particles, the free energy can be
engineered by tuning the electron state density of active
atoms with chemical bonding [124]. Isolated single Pt atoms
anchored on g-C3N4 have been used as a new form of co-
catalysts to enhance the H2 evolution through photocatalytic
activity. Pt single atoms on the g-C3N4 can modulate the
electronic structure which leads to an increase in the photo-
generated electrons’ lifetime. This happens because the iso-
lated Pt atoms induce changes in the surface trap states. The
photocatalytic H2 generation performance enhances up to 50
times the bare g-C3N4 [130].
Defect engineering
The introduction of defects in g-C3N4 heterostructures can
alter light harvesting, charge isolation and migration, and the
kinetics of surface reactions that could lead to enhanced
photocatalytic activity [131]. The introduction of defects in-
cludes the introduction of vacancies into the structure of the
g-C3N4, nitrogen vacancies, amorphization, dye, cyanamide
defects, breaking of hydrogen bonds, alkalinized treatment,
oxygenation, vacuum heat treatment, protonation, and
reducing defects [132]. For example, the creation of vacancies
can greatly amend the photocatalytic activity of the g-C3N4 by
the creation of midgap states and altering the band gap energy
to convert photons with a longer wavelength. Vacancy defects
act as capturing sites to foster charge isolation and migration.
The two-dimensional characteristics of g-C3N4 facilitate the
introduction of defect sites in its structure. The creation of
vacancies can promote both donor and acceptor sites which
can lead to the dissociation of charge carriers [133].
A brief comparison between different g-C3N4
heterojunctions
The most simple types of heterojunctions are type I, type II,
and type III with a straddling gap, staggered, and broken gap,
respectively. In the type I heterojunctions (Fig. 11a), the CB
and VB of one semiconductor (A) are higher and lower than
the other semiconductor (B) bands, respectively. Conse-
quently, when the heterojunction is irradiated, the holes and
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8 32723

Fig. 11 e Schematic illustration of the separation of electronehole pairs in conventional heterojunction photocatalysts: (a)
type-I, (b) type-II, and (c) type-III, d) supposed path and e) real path electron transfer path in all-solid-state Z-scheme
photocatalyst through the solid conductor. Adapted with permission from Ref. [134] Copyright (2017) WILEY-VCH Verlag
GmbH & Co. KGaA, Weinheim.

electrons will be accumulated at the VB and CB of the semi-
conductor B, respectively. Therefore, the charge carriers
accumulation happens in one semiconductor and hence, the
charge separation is hindered. Furthermore, the redox reac-
tion occurs on the semiconductor that possesses a smaller
redox potential. This will decrease the photocatalytic perfor-
mance of the heterostructure. In type II (Fig. 11b), the VB and
CB of one semiconductor (A) are higher than those of the other
semiconductor (B). Therefore, the photogenerated electrons
will be accumulated in semiconductor B and holes will
migrate to semiconductor A. Despite charge separation in type
II heterojunctions, similar to type I, the redox ability is
decreased since the reduction and oxidation reactions occur
on semiconductor B with a lower reduction potential and on A
with a lower oxidation potential, respectively. Type III is
similar to type II (Fig. 11c), but the staggered gap is large
enough to prevent overlapping of the band gaps. Since the
charge carrier separation between two semiconductors can
not occur in type III heterojunction, it is not an efficient type
for photocatalytic reactions. Thus, among the aforementioned
types of heterojunctions, type II is preferred for charge carrier
separation and improved photocatalytic activity [134].
As discussed in Section 6, due to the shortcomings of the
traditional Z-scheme heterostructures, all-solid-state Z-
scheme heterojunctions have been developed. The applica-
tion of this type has been widely developed due to the
replacing the shuttle ion pairs with solid conductors (e.g. Pt
and Au). However, as can be seen in Fig. 11dee, the supposed
32724 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 8 ( 2 0 2 3 ) 3 2 7 0 8 e3 2 7 2 8
charge transfer between semiconductors is incorrect. The
electrons in S2 with a greater reduction ability are prone to
recombine with the holes in S1 through the path of the solid
conductor. Thus, the electron transfer depicted in Fig. 11e is
easier than in Fig. 11d [135].
However, in the S-scheme heterostructures, as discussed
in Section 7in this article, the powerful photogenerated holes
and electrons are reserved in the VB of OP and CB of the RP,
respectively; while weak photogenerated electrons and holes
are recombined. Thus, in this type of heterostructure, strong
redox ability can be obtained by preserving powerful charge
carriers [54,135].
Challenges and future prospective
The g-C3N4 is one of the emerging photocatalysts that has
several advantages over traditional TiO2 photocatalysts
including visible light response and easy synthesis. However,
the high rate of charge carrier recombination in g-C3N4 has
hindered its wide application in its pristine form. Several
strategies have been applied to overcome the g-C3N4 short-
ages, including the application of a co-catalyst, surface engi-
neering, crystalline manipulation, elemental doping, and
construction of a heterostructure. For maximum light ab-
sorption, the bandgap of the semiconductor should be narrow.
On the other side, the VB and CB of the photocatalyst should
be located at energy levels more positive and more negative,
respectively, to effectively impart in the redox reactions. This
needs a higher bandgap. Therefore, both these criteria cannot
be satisfied in a single-component photocatalyst. The con-
struction of a heterostructure can improve photocatalytic
performance by better charge separation in the photocatalyst.
Several types of g-C3N4/semiconductor heterostructures
including type II, Z-scheme, and S-scheme heterostructures
have been developed recently. The charge transfer path in the
heterostructure determines the type of the heterostructure.
Despite recent advances in the construction of different types
of geC3N4ebased heterostructures, some issues need to be
addressed.
Density functional theory studies on heterostructures are
limited. However, the study of the electronic structure of the
heterostructures can help to realize and predict emerging
heterostructures for improved photocatalytic performance
and charge separation.
The charge transfer path in some of the heterostructures is
not clear. More experiments are needed to clarify the true
charge path.
The effect of the defects, vacancies, and doped elements on
the electronic structure of the heterostructures should be
investigated for different heterostructures. The effect of the
defects and doped elements on photocatalytic performance is
not clear in many substances. It should be responded that
what is the optimum fraction of the defects for enhancing
photocatalytic performance if the defects are beneficial.
The intimate contact of the heterostructure components is
necessary for charge transport. Strategies for better intimate
contact between the heterostructure components need to be
studied.
While several types of heterostructures are made, the ef-
fect of dimensions (i.e., 0D, 1D, or 3D structures) on charge
transfer has not been investigated for many of them. The
morphology of the components also affects the charge
transfer and photocatalytic performance. Therefore, different
morphologies and dimensions should be constructed for the
previously studied heterostructures and their photocatalytic
performance should be investigated.
It seems that due to the inherent characteristics of g-C3N4
photocatalyst, if the mentioned issues are reached their op-
timum conditions, C3N4-based photocatalysts can solve many
of the environmental- and energy-related problems such as
degradation of pollutants and H2 production.
Availability of data and materials
The datasets used and/or analyzed during the current study
are available from the corresponding author upon reasonable
request.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgment
The author would like to appreciate the Shahrood University
of Technology and the Iranian Nanotechnology Initiative
Council for their financial support of this project.
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