Coordination Chemistry Reviews 500 (2024) 215489

Contents lists available at ScienceDirect

Coordination Chemistry Reviews

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

Review

The progress of g-C3N4 in photocatalytic H2 evolution: From fabrication

to modification
Dandan Ma 1, Zhuoming Zhang 1, Yajun Zou, Jiantao Chen, Jian-Wen Shi *
State Key Laboratory of Electrical Insulation and Power Equipment, Center of Nanomaterials for Renewable Energy, School of Electrical Engineering, Xi’an Jiaotong
University, Xi’an 710049, China

A B S T R A C T

Polymeric semiconductor, Graphitic Carbon Nitride (g-C3N4), has emerged as one of the desired materials in photocatalytic hydrogen evolution (PHE) due to its
visible-light activity, facile accessibility, low-cost, chemical stability, as well as the unique layered structure. However, pure g-C3N4 photocatalyst suffers from limited
photocatalytic performance due to the low efficiency of charge carrier separation and serious charge recombination. Researches over the past few decades have
shown that the photocatalytic active of g-C3N4 can be easily affected by many factors including spatial morphology, electronic structure, as well as the interaction
between g-C3N4 and other materials. This review gives a comprehensive introduction over the basic properties and the development of g-C3N4 in PHE. A brief history
and the basic properties are firstly introduced. After then, this review introduces the fabrication and the limits of g-C3N4 in PHE, followed by the rational methods in
improving the photocatalytic active of g-C3N4 including the self-modification strategies (e.g., molecular structure regulation, defect engineering and microstructure
manipulation) and the exogenous modification strategies (e.g., the deposition of co-catalyst and the construction of g-C3N4 based heterostructure). Lastly, this review
discusses the major challenges and opportunities of g-C3N4 in photocatalytic field. It is believed that this review is benefit for proposing more effective solutions in
developing high active g-C3N4 photocatalysts based on a comprehensive understanding of g-C3N4 material.

1. Introduction
Since the industrial revolution, the high consume of fossil fuels and
the immoderate emissions of carbon dioxide are pushing the Earth into
the abyss of environmental degradation and resource depletion, which
bring a serious threat to the survival and development of human being
[1–3]. In face of the increasingly severe global climate and energy crisis,
exploring and developing renewable green energy is extremely urgent.
As one of the most important secondary energy sources, hydrogen (H2)
energy is a promising alternative of the traditional fossil energy, and has
attracted strong researches in addressing the global energy and envi­
ronmental issues due to the irreplaceable merits, such as clean (zero
carbon emission from the combustion process), high energy density
(calorific value: 120–142 MJ/kg), diverse sources (water splitting)
[4–6], and so on.
Despite the charming merits of hydrogen energy itself, the reason­
able production of hydrogen with the minimize carbon emission is still a
key factor in constructing an eco-friendly renewable energy system. As
shown in Fig. 1, among different hydrogen-production strategy, the
“green hydrogen” is most expected. The named “green hydrogen” is to
produce hydrogen with “zero carbon emission” through the use of
renewable energy, which not only avoids the negative impact on envi­
ronment caused by the use of fossil fuels, but also provides solution for
the long-term energy storage of renewable energy [7,8], thus is of great
significance in integrating the development of multiple energy sources
and improving the efficiency of energy system utilization.
Up to now, scientists have reported several approaches to produce
hydrogen through the renewable energy strategies [3–5]. From the
perspective of energy utilization efficiency and sustainable develop­
ment, semiconductor-based photocatalytic hydrogen evolution (PHE)
from water splitting can directly convert solar energy into hydrogen
energy, which minimizes the energy loss in the energy transfer pro­
cedure and thus has great potential in the production of “green
hydrogen” [5–7]. However, despite the mass of efforts, it is a pity that
the most of the current reported photocatalytic systems are unable to
meet the needs of practical hydrogen production, mainly due to the
limited photocatalytic activity and the poor photo stability of photo­
catalysts[9–11]. The exploration and design of photocatalysts with high
activity and stability are still the key step to realize industrial PHE.
In recent years, graphitic carbon nitride (g-C3N4) has become an
attractive research hotspot in the exploration of high performance
photocatalysts [10–14], more than 6900 research articles focused on the

* Corresponding author.
E-mail address: jianwen.shi@mail.xjtu.edu.cn (J.-W. Shi).
1
These authors contributed equally to this work.

https://doi.org/10.1016/j.ccr.2023.215489
Received 31 March 2023; Accepted 11 October 2023
Available online 2 November 2023
0010-8545/© 2023 Elsevier B.V. All rights reserved.
D. Ma et al.
g-C3N4 based PHE region have been published in the past ten years
(Fig. 2). The continuous climbed number of research papers over the
past 10 years indicates an increasing research interest in g-C3N4 based
PHE, and the slight declined data in 2022 possibly due to the hampered
research caused by the global COVID-19 pandemic. Although scientists
have placed high expectations on the photocatalytic performance of g-
C3N4, the photocatalytic activity and stability of traditional g-C3N4 are
still far away from the demands of practical application, which is mainly
because of the intrinsic serious charge recombination and low efficient
surface reaction rate in g-C3N4 [11–13], greatly hindering the applica­
tion of g-C3N4 in photocatalysis. In order to improve the photocatalytic
performance of g-C3N4 as much as possible to make it competitive in
photocatalytic reaction, various methods, including ontology doping,
surface modification, structure design, the construction of hetero­
structures, and so on, have been adopt.
Thus, this review tries to provide a comprehensive description and
details analysis about the accomplishments of g-C3N4 in PHE and put
forward possible strategies in driving the shortcomings in the current
study. First of all, we introduce the basic principle of semiconductor
based photocatalysis. Secondly, the development history and basic
properties of g-C3N4 are described. Thirdly, the preparation and appli­
cation status of g-C3N4 in PHE are discussed. Fourthly, the current
developed strategies in improving the photocatalytic performance of g-
C3N4 are summarized. Finally, the current challenges and future de­
velopments of g-C3N4-based photocatalysts are discussed.
2. The basic principle of PHE
Researchers would realize the substantial improvement of its cata­
lytic performance in essence only on the basis of in-depth understanding
of the catalytic mechanism of semiconductor based photocatalysis. Since
Fujishima and Honda reported the PHE experiment in 1973 [14], sci­
entists have put a lot of efforts to reveal the basic principle of PHE. A
semiconductor-based photocatalysis refers to the process of accelerating
the surface REDOX reaction through a light-irradiated semiconductor,
where the photogenerated electrons ( e− ) and holes (h+), named charge
carriers, play crucial roles in participating the REDOX reaction [15].
According to the solid energy band theory, the band structure in semi­
conductors is discontinuous, that is, there are high-energy bands (Con­
duction Band, CB) that are not filled by electrons and low-energy bands
(Valence Band, VB) that are filled by electrons, and the energy level
Fig. 1. (a) Schematic diagram of hydrogen production technology route, (b) Schematic diagram of the renewable energy based H2 evolution procedure.
2
Coordination Chemistry Reviews 500 (2024) 215489
region between CB and VB is named forbidden band [12,13]. When a
semiconductor is irradiated under simulated sunlight and excited by the
photons whose energy is greater than or equal to its band-gap width (Eg)
energy, the electrons will jump from the VB to the CB, leaving corre­
sponding holes in VB to form the electron (e− ) - hole (h+) pairs. The
photogenerated electron-hole pairs subsequently separate and migrate
to the surface-active sites of catalyst, where the electron acceptor is
reduced by the photogenerated electrons and the electron donor is
oxidized by the photogenerated holes. It should be mentioned that,
during the migration of photogenerated charge carriers, the electron-
hole in close proximity will recombine due to electrostatic interaction
in the bulk phase or surface of the material and release energy in the
form of light or heat, which is harmful to the photocatalysis due to the
reduced utilization of photogenerated carriers [11,15].
As shown in Fig. 3, the mechanism of photocatalysis can be short­
ened to three steps: 1) The formation of photogenerated electron-hole
pairs. Semiconductors absorb the proper incoming sunlight and are
excited to produce photogenerated electrons and holes. This procedure
occurs on a relative fast time scale in femtosecond (fs) range; 2) The
transfer of electron-hole pairs. The photogenerated electrons and holes
transfer to the surface of semiconductor, in which the charge transfer
and recombination occur at the same time. The separation and transfer
of charge carriers happen in picosecond (ps) to microseconds (μs) scale
while the charge recombination happens in ps to millisecond (ms); 3)
Surface REDOX reaction. Reactants adsorb on the surface of semi­
conductors and respectively react with electrons and holes, and the
photocatalytic reactions occur in μs to ms range [16,17]. Based on the
basic time scale difference of the charge carriers from generation to
surface reaction, it can be concluded that the PHE efficiency depends on
the competitive procedure of charge transfer and charge recombination.
Considering that the charge transfer happens in a faster time scale than
that of charge recombination, the key in improving PHE is to facilitate
the rapid separation and transfer of charge carriers and avoid their bulk/
surface recombination [15–17]. It is to say, the photocatalytic perfor­
mance can be improved through decreasing the bulk size or increasing
the specific surface area of semiconductor, speeding up the separation of
charge carriers, as well as accelerating surface reaction.
3. g-C3N4 photocatalyst
As a new type of non-metallic organic semiconductor photocatalyst,
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 2. Annual publications details based on g-C3N4 photocatalyst utilized in PHE reaction from 2009 to 2022 (Adapted from ISI Web of Science, dated 28th
March 2023).

Fig. 3. The difference of photocatalysis in time scale and spacial scale. Adapted with permission from ref. [17]. Copyright 2020 Royal Society of Chemistry.

Graphitic Carbon Nitride (g-C3N4) has attracted increasing researches in
the past decades due to the unique electronic structure, visible light
response and excellent chemical stability. The design and modification
of g-C3N4-based photocatalytic system is a research hotspot in the con­
struction of highly efficient photocatalyst [19–22].
3.1. The brief research history of g-C3N4
Graphitic carbon nitride (g-C3N4) is a tri-s-triazine repeating unit
stacked organic semiconductor with a graphitic p-conjugated structure.
As an eldest polymer with general formula of (C3N3H)n, it has received
extensively researches over the last hundred years [22,23]. The earliest
research on C-N compounds can be traced back to 1834, when Berzelius

3
D. Ma et al.
synthesized a carbon and nitrogen compound composed of heptazine
structural units in laboratory, which was named “Melon” by Lepzig [24].
In 1922, Franklin obtained an amorphous carbon–nitrogen compound
by pyrolysis of mercuric thiocyanate and put forward the concept of
“carbonitride” for the first time [25]. Due to the fact that g-C3N4 is
chemical inertness and insolubility in most solvents, it is difficult to
determine the crystal structure of carbon nitride, and research on this
material has been at a standstill. In 1937, based on the X-ray crystal­
lography study, Pauling and Sturdivant declared that a coplanar tri-s-
triazine unit was the basic elementary structural unit of all polymeric
g-C3N4 derivatives [26]. In 1982, the coplanar arrangement reported by
Pauling and Sturdivant was confirmed by Leonard and co-workers after
they successfully prepared the single crystal structure of cyameluric
derivatives (C6N7H3) through a bottom-up assembly strategy [27].
When time came to 1989, Cohen et al. simulated the structure of β-C3N4
through calculation and predicted that the material had a hardness
comparable to diamond, which once again stimulated researchers’
enthusiasm for the study of carbon nitride [28]. In 1996, Teter et al.
proposed that carbon nitride has five different crystal structures: α
phase, β phase, quasi-cubic phase (P phase), cubic phase (C phase) and
graphite phase (G phase) (Fig. 4) based on theoretical calculation [29].
Among them, g-C3N4 has the highest stability at normal temperature and
pressure, and has semiconductor properties. In 2006, Goettmann et al.
applied g-C3N4 for the first time in the photocatalytic decomposition of
aquatic hydrogen driven by visible light [30]. Immediately, in 2009,
Wang at al. found that g-C3N4 displayed encouraging active under
visible light irradiation for the first time [31], which marks a great
milestone in the research of metal-free organic photocatalysts.
Compared with traditional inorganic semiconductor photocatalysts,
organic semiconductor photocatalyst g-C3N4 has many advantages, such
as good chemical stability, adjustable electronic structure, n-type
semiconductor features, earth-abundant and so on [16–19]. All of these
merits have extremely boomed the flourishing study on the g-C3N4-
based photocatalysts.
3.2. The structure and physicochemical properties of g-C3N4
As shown in Fig. 5a, the pure g-C3N4 is pale yellow solid power with
the light absorption band edge at 475 nm, and the absorption band edge
can be slightly affected by different preparation conditions, such as the
Fig. 4. Five different crystal phases carbon nitride. Adapted with permission from ref [29]. Copyright by 2016 Acta Physico-Chimica Sinica.
4
Coordination Chemistry Reviews 500 (2024) 215489
selection of reaction precursor and the control of calcination tempera­
ture. In addition, the C/N structure of g-C3N4 conjugate endows the
semiconductor with fluorescence characteristics with the emission peak
at around 470 nm, and the fluorescence lifetime is in the range of 1–5 ns.
Similar to that of light absorption ability, the fluorescence characteris­
tics also changes with the prepare strategy and the layer of g-C3N4
nanosheet (NS). The fluorescence quantum yield of g-C3N4 prepared by
traditional thermal condensation polymerization method is less than 5
%, and it needs to be stripped to form ultra-thin nanosheets (NSs) to
have applicable fluorescence properties [31,32].
In terms of microstructure, g-C3N4 has a graphite-like layer structure,
the aromatic heterocyclic structure inside the layers and the van der
Waals force between the layers endow g-C3N4 with good chemical and
thermal stability. In general, under the protection of inert gas, g-C3N4
can be broken down only when the material is heated up to more than
450 ℃, while it can still remain stable when it is heated to as high as 600
℃ in the air [33–36]. What’s more, the graphite-like layer structure
endows the g-C3N4 with extremely large specific surface area, which is
calculated to be as high as 2500 m2/g for ideal monolayer g-C3N4 sample
[37].
g-C3N4 is a widely studied C-N polymer characterized by the typical
two-dimension graphite-like topological structure. The ground state
structure of g-C3N4 is mostly studied by using X-ray diffraction method.
As shown in Fig. 5b, the two typical XRD peaks located at 2θ = 13.0◦ and
27.4◦ respectively arise from the in-plane repeated unit with a distance
of about 6.81 Å and the graphitic interlayer with a distance of 3.26 Å
[31]. However, limited by the experimental conditions and character­
ization techniques, the relative position of C and N atoms in the
graphite-like structure can be only predicted through theoretical
calculation and exact stacking positions of C and N atoms are still not
clear now.
It is generally believed that there are two types of basic structural
units of g-C3N4: the R3m spatial group crystal structure formed by the
Triazine ring (C3N3, triazine) and the P6m2 spatial group crystal struc­
ture formed by the Heptazine ring (C6N7, Tri-S-Triazine or Heptazine)
[38–40]. As shown in Fig. 6, R3m and P6m2 structure g-C3N4 display
different energy states due to the difference in the size of the nitrogen
holes and the chemical environment of the nitrogen atoms in the allo­
trope. Based on density functional theory (DFT) calculation, Kroke et al.
[32] found that the binding energy of the Heptazine unit is lower than
D. Ma et al.
Fig. 5. (a) Optical absorption properties and optical photographs of g-C3N4, (b) Crystal structure of g-C3N4 obtained from XRD measurement. Adapted with
permission from ref [31]. Copyright 2009 Macmillan Publishers Limited.
Fig. 6. Two basic structural units of g-C3N4.
that of the Triazine unit, so the structure of the Heptazine unit is more
stable. Therefore, it is generally believed that g-C3N4 is composed of
Heptazine structural units.
As an organic semiconductor photocatalyst, the studies on the elec­
tron structure and energy band distribution of g-C3N4 are also attractive.
As shown in Fig. 7, in the common studied two-dimensional g-C3N4, C
and N atoms are distributed in one plane and form hexagonal structure
through σ bond, while the lone pair electrons in the Pz orbitals of the C
and N atoms form a highly delocalized π-conjugated framework due to
the sp2 -hybridization [40,41]. Among them, the formation of π-conju­
gated framework is believed to be the origin of photocatalytic reactivity
of g-C3N4 [39–42].
Based on theoretical studies, the lone pair electrons of N atom are
mainly responsible for the formation of Highest Occupied Molecular
Orbital (HOMO) while the lone pair electrons of C atom constitute the
Lowest Unoccupied Molecular Orbital (LUMO), which corresponds to
the VB and CB in the semiconductor, respectively. The bandgap de­
creases from 3.5 eV to 2.1 eV with the stack of g-C3N4 NSs from several
layers to one layer. The exact band gap of g-C3N4 can be evaluated from
the ultraviolet–visible spectrum with a semiconductor-like absorption
characteristic (about 2.7 eV), which is sufficiently large to overcome the
endothermic character of the water-splitting reaction (Fig. 8)
[31,44–49].
4. Preparation of g-C3N4
Many researchers are committed to the preparation of g-C3N4. In
5
Coordination Chemistry Reviews 500 (2024) 215489
total, g-C3N4 is mainly prepared through the “bottom-up” method by the
polymerization of N-rich precursors (such as urea, cyanamide, dicyan­
diamide, melamine, thiourea, and so on) and the “top-down” method by
peeling from bulk material through the chemical or physical methods.
The main pathway of “bottom-up” synthesis methods includes thermal
condensation polymerization, solvothermal method, solid phase reac­
tion method, vapor deposition method, electrochemical deposition
method, and so on, while exfoliation method is the mostly used “top-
down” strategy. Table 1 lists the advantages and disadvantages of each
method, followed by a detailed introduction to commonly used
methods.
4.1. Thermal condensation polymerization method
Urea, cyanamide and dicyandiamide are the mostly used precursors
in the direct pyrolysis method. The g-C3N4 can be easily prepared
through the polycondensation during a simple heating and heat pres­
ervation procedure. The heating temperature affects the structure and
photocatalytic performance of g-C3N4 directly [50–54]. Yan et al. [50]
obtained g-C3N4 with good crystallization by directly calcination of
melamine at 500–580 ◦ C, it was found that the ration of C/N in g-C3N4
can be adjusted through the control of heating temperature, which
induced a continuous changed value of forbidden band energy. Zhang
et al. [51] fabricated g-C3N4 by directly heating thiourea in air and
investigated the effect of reaction temperature on the structure of g-C3N4
product. An improved degree of polycondensation and polymerization
of g-C3N4 was detected when the calcination temperature gradually
D. Ma et al.
Fig. 7. Predicted images of heptazine-based g-C3N4, (a) predicted most stable configuration, phase 1, (b) second stable distorted configuration, phase 2, (c) most
stable planar configuration, phase 3. The atoms in the middle layer of the lattices are labeled with yellow crosses. Adapted with permission from ref [43]. Copyright
2017 American Chemical Society.
increased from 450 to 600 ◦ C, indicating an enhanced delocalization of
electrons in aromatic sheets, which can be ascribed to the fact that the
improved reaction temperature benefits to the formation of stronger van
der Waals interaction forces between the tri-s-triazine cores and thus
facilitating the tri-s-triazine packing units, which further promotes the
photocatalytic redox ability of the sample [52].
The effect of heating time on the formation of g-C3N4 has also been
widely studied [55–59]. For example, Dong et al. [55] heated urea at
550 ◦ C with an increasing reaction time from 0 to 240 min, and they
found that the specific surface area of g-C3N4 gradually increased from
31 to 288 m2/g, while the layer thickness decreased from 36 to 16 nm.
The thermal condensation polymerization method of g-C3N4 has
been concerned by scientists. In 2009, Wang et al. [31] reported the
thermal condensation polymerization method of g-C3N4 prepared by
using mono-cyanamide as a precursor. As shown in Fig. 9, the mono-
cyanamide was firstly condensed into dicyandiamide when the mono-
cyanamide precursor was heated to 150 ◦ C, which further poly­
condensated to melamine when the heating temperature was further
increased to 240 ◦ C. At a temperature of 390 ◦ C, cyanamide thermally
polymerized to form heptazine structural unit (also known as mel­
amine). As the temperature rising to more than 520 ◦ C, g-C3N4 with high
polymerization degree was gradually formed.
Besides, some assistant strategies such as template method and acid
treatment method are also combined with the traditional thermal
condensation polymerization method to fabricate the g-C3N4 with spe­
cial structure and morphology [60–63]. Zhong et al. [60] fabricated g-
C3N4 by using the HNO–3 protonated melamine as precursor to create
extra porous structure. Due to the decomposition of protonated mel­
amine, the as-prepared g-C3N4 displayed a highly porous structure,
which contributes to a lower recombination rate of charge carriers.
Zhang et al. [61] fabricated acidified g-C3N4 via a one-step process by
pretreating HCl and alcohol with melamine. The obtained g-C3N4
6
Coordination Chemistry Reviews 500 (2024) 215489
exhibited a belt- and ribbon-like morphology and comprised aggregated
bundles or cables with numerous voids and higher surface-to-volume
ratio than those of pristine g-C3N4.
There is no doubt that the thermal condensation polymerization
method has many attractive advantages such as facile to fabrication, cost
effective, and high production yield, which are benefit to large-scale
industrial production. Deficiently, it has been found that the photo­
catalytic property of the g-C3N4 fabricated via direct pyrolysis of N-rich
precursors is weak, this is because that a various of intermediates formed
at the high reaction temperature, and the formed intermediates are
difficult to be completely dislodged due to the incomplete poly­
condensation, which results in a disordered g-C3N4 structure and the fast
recombination of the photogenerated electron-hole pairs [63].
4.2. Solvothermal method
In solvothermal method, C and N precursors are added into a high-
pressure steel reactor containing high boiling point organic solvent as
the heat conduction medium, and then heated up to a certain temper­
ature. Thus, g-C3N4 can be obtained in the high-temperature and high-
pressure environment [64–66]. Montigaud et al. [65] synthesized g-
C3N4 micro particles through solvothermal method by using tri­
chlorohydric acid and melamine as precursors and triethylamine as
solvent at 250 ℃ reaction condition. Using melamine and melamine
chloride as precursors and acetonitrile as solvent, Cui et al. [66] pre­
pared g-C3N4 nanorods with uniform shape at 140–180 ℃ for 24–96 h.
By contrast, the g-C3N4 prepared by solvothermal method usually suffers
worse crystallinity than that prepared by thermal condensation poly­
merization. However, the advantages of mild conditions, simple oper­
ation and uniform and controllable product morphology also make the
solvothermal method popular and important in preparing g-C3N4 with
special morphology and special structures.
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 8. The electronic structure diagram of g-C3N4 calculated by DFT. Adapted with permission from ref [31]. Copyright 2009 Macmillan Publishers Limited.

harsh reaction conditions, the reaction course is complex and the

Table 1
product generally contains graphite carbon impurities, this method is
Comparison of the advantages and disadvantages between different methods in
regarded to have weak practicability in preparing g-C3N4.
the fabrication of g-C3N4.
Synthesis method Advantages Disadvantages
4.4. Vapor deposition method
Thermal condensation High yield, and high Time consuming
polymerization crystallinity, produced g-
Generally, C-based and N-based organic compounds are utilized as
method C3N4 with tunable
structure raw reaction materials in vapor deposition. Under heating or other
Solvothermal method Easy to operate, eco- Low yield and long conditions, the organic precursors are decomposed into small molecules
friendly and low cost synthesis cycle and then polymerizes to generate g-C3N4 [70–73]. Xiao et al. [70] adopt
Solid-phase reaction High crystallinity and high Time- and cost-consuming
vapor deposition method using melamine as raw material to obtain flat
method yield and complicated
preparation process
g-C3N4 film on glass substrate. The obtained g-C3N4 film is about 250 nm
Vapor deposition Good yield, high purity High cost, complicated in thickness and can be independently self-supporting after peeling. g-
method steps, limited crystallinity C3N4 obtained by vapor deposition has a smooth and uniform structure,
Electrochemical Good yield, simple steps, Low purity which makes this method attractive in the fabrication of g-C3N4 films,
deposition method controllable thickness
and it is also an important tool to in-situ growth g-C3N4 on other semi­
Exfoliation method High crystallinity, high Environmentally
purity and thinner layer unfriendly, low yield conductor substrates. By using vapor deposition method, Gao et al. [71]
deposited g-C3N4 on TiO2 nanoarray substrate to form closely contacted
heterostructure.
4.3. Solid-phase reaction method
4.5. Electrochemical deposition method
In the solid-state reaction method, g-C3N4 is obtained by mixing C
precursor and N precursor uniformly and then treating with high tem­
Electrochemical deposition is a method of growing g-C3N4 on elec­
perature and pressure without the addition of organic solvent [67–69].
trode substrate with C and N-based organic solution as raw materials
Sekine et al. [67] obtained sheet-like g-C3N4 by treating C6N4 and
under the addition of extra potential. By using the electrochemical
triazine precursors at 1400 ◦ C and 5 GPa for 30 min. Similarly, by using
deposition method at the applied potential of 5 V, Lu et al. [74] prepared
melamine and hydraine as reactants and calcinating at 800 ◦ C and 3 GPa
g-C3N4 NSs with thickness of 2 nm by using melamine and sodium hy­
environment, Alves et al. [68] obtained g-C3N4 with good crystalliza­
droxide aqueous solution as electrolyte. Zhao et al. [75] reported the
tion. Considering that the solid phase reaction method usually requires
fabrication of layer g-C3N4 by using dicyandiamide as a precursor, and

7
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 9. Schematic diagram of the thermal condensation process of g-C3N4 prepared with mono-cyanamide as precursor. Adapted with permission from ref [19].
Copyright 2016 American Chemical Society.

the g-C3N4 grown on the electrode within 10 s by microwave-assisted 4.6. Exfoliation method
electrochemical deposition. The electrochemical deposition method
has been widely used in the preparation of g-C3N4 thin films due to its Inspired by the exfoliation of graphene, many kinds of exfoliation
simple operation, high generation speed and low reaction temperature. strategies, such as ultrasonication assisted liquid exfoliation method,

Fig. 10. Morphology of g-C3N4 prepared by using (a) Thermal condensation polymerization method. Adapted with permission from ref [51]. Copyright 2012
Elsevier. Adapted with permission from ref [52]. Copyright 2018 Springer. Adapted with permission from ref [63]. Copyright 2018 Korean Society of Industrial
Engineering Chemistry. (b) Solvothermal method. Adapted with permission from ref [64]. Copyright 2019 Institution of Engineering and Technology. Adapted with
permission from ref [66]. Copyright 2016 Wiley. (c) Solid-phase reaction method. Adapted with permission from ref [69]. 2019 Institution of Engineering and
Technology. (d) Vapor deposition method. Adapted with permission from ref [70]. Copyright 2018 Wiley. Adapted with permission from ref [71]. Copyright 2016
Wiley. Adapted with permission from ref [72]. Copyright 2020 Elsevier. Adapted with permission from ref [72]. Copyright 2020 Elsevier. (e) Electrochemical
deposition method. Adapted with permission from ref [74]. Copyright 2015 Royal Society of Chemistry. Adapted with permission from ref [75]. Copyright 2019
Wiley. (f) Exfoliation method. Adapted with permission from ref [78]. Copyright 2022 Springer.

8
D. Ma et al.
thermal exfoliation method, chemical exfoliation method, and so on,
have been used for the fabrication of g-C3N4 from the bulk material
[76–78]. Liu et al. [76] reported the facile fabrication of few-layered
porous g-C3N4 nanoplates by using a novel combination of thermal
etching and gas-driven exfoliation of bulk g-C3N4, and the obtained few-
layered porous g-C3N4 nanoplates displayed modified electronic struc­
tures, large specific surface area, as well as greatly enhanced photo­
catalytic activities. Rono et al. [77] compared the photocatalytic
performance of the g-C3N4 NSs obtained by thermal etching and liquid
exfoliation of bulk g-C3N4. The g-C3N4 NSs prepared by thermal exfoli­
ation method displayed a smaller specific surface area, but it presented
much higher photocatalytic activity than that synthesized by liquid
exfoliation. The reason can be ascribed to the porous structure formed
during the thermal treatment procedure. Zheng et al. [78] fabricated g-
C3N4 by using a gas exfoliation method and studied the exfoliation
mechanisms by combing experiments and theoretical calculation, it was
revealed that the liquid nitrogen molecules entered the edge space in g-
C3N4 layers and subsequently pushed deeper, finally resulted in the
exfoliation of NSs.
Fig. 10 displays some typical morphology of g-C3N4 fabricated by
different methods. It can be observed that the traditional thermal
condensation polymerization method and solvothermal method are
more likely to endow g-C3N4 with loose 2D morphology or bulk feature.
In the deposition strategies, the morphology of g-C3N4 depended on the
substrates and the thickness of g-C3N4 can be controlled by the deposi­
tion procedure. In addition, the single layer and low layer numbers of g-
C3N4 can be obtained from the exfoliation method. Based on the
different characterizations of these several methods, researchers can
control the morphology and structure of g-C3N4 by choosing proper
fabrication strategy.
5. Limits of g-C3N4 in PHE
In recent years, researchers have made a series of substantial prog­
ress in the application of g-C3N4 in PHE, but the efficiency of PHE is still
far away from the practical application requirements. Although g-C3N4
has good thermal and chemical stability, it also has some problems as a
photocatalyst: (1) The serious charge recombination in large size bulk g-
C3N4 results in a low utilization efficiency of photogenerated carriers;
(2) The exposure of reaction active site and the mass transfer process are
easily limited by the specific surface area; (3) Limited visible light ab­
sorption leads to insufficient visible light response; (4) Inadequate
expansion of π-conjugate system results in poor electrical conductivity,
high exciton binding energy and low quantum efficiency. All of the
above-mentioned shortcomings make the pure g-C3N4 an unsatisfied
photocatalytic performance and limit its practical application. There­
fore, the modification of g-C3N4 is necessary to drive the development of
g-C3N4 in PHE [78–81].
Additionally, as a typical REDOX reaction, the PHE activity of g-C3N4
is also directly affected by the environmental factors, such as pH, tem­
perature, as well as the addition amount of catalyst. Among, pH value of
reaction solution is the most concerned factor in affecting the photo­
catalytic activity because the functional groups on the surface of g-C3N4
are easily affected by the environmental pH value and thus changing the
density and delocalization of electrons [79–81]. Wu et al. [79] discussed
the effect of pH and methanol on the PHE performance of g-C3N4, and
they found that the alkaline environment and the addition of methanol
would accelerate the transfer of photogenerated holes into solution and
thus benefit to the PHE reaction of g-C3N4. Otherwise, the addition
mount of photocatalysts is another worth noticed factor discussing the
PHE activity of the photocatalysts. It has been found that the H2 evo­
lution rate exhibited liner increase with the increased amount of pho­
tocatalyst in a narrow mass range, while the over addition of
photocatalyst resulted in a very slow increase or even decline in pho­
tocatalytic activity, this is because the absorption of irradiation light was
shield when too much solid catalyst was added in the solution [77,78].
9
Coordination Chemistry Reviews 500 (2024) 215489
In addition, some other factors, such as the thermal effect generated
under light irradiation [80], has also been noticed in some literatures.
The effects of all these factors on the photocatalytic process are complex
and need to be further studied. In order to give out an objective and
accurate evaluation to the real PHE performance of g-C3N4, the photo­
catalytic measurements are usually carried out under a stable environ­
ment, such as keeping the same sacrificial agents, the same light power,
the same addition amount of catalyst, and so on.
From the basic principle of PHE, the photocatalytic performance of g-
C3N4 can be improved from the following perspectives: (i) improving the
generation of photogenerated charge carriers by expanding the light
absorption range of photocatalysts, (ii) accelerating the charge migra­
tion and separation and suppressing the harmful charge recombination
rate, (iii) increasing the exposure of active sites and decreasing the re­
action energy barrier to facilitate the utilization of charge carriers, (iv)
improving the photo-stability of the photocatalysts through inhibiting
the photo-corrosion [82–85]. Up to now, many strategies, including
defect engineering, surface modification, size and morphology control,
co-catalyst deposition and the construction of heterostructures, have
been proposed to alleviate the influence of the adverse factors and
improve the photocatalytic performance of g-C3N4, which will be dis­
cussed more detailed in the following sections.
6. Self-modification of g-C3N4
The hot research of PHE technology has stimulated diverse strategies
in the modification of g-C3N4. In this review, the modification strategies
are mainly classified into two major categories: self-modification and
exogenous modification. It is to say, one approach is to change the
inherent properties of g-C3N4 to accelerate the PHE process and the
other strategy is to introduce an assisted material to speeding up the
generation of hydrogen without changing the properties of g-C3N4 itself.
The evaluation indexes of g-C3N4 semiconductor photocatalysts mainly
include the morphology, crystal phase, crystallinity, shape, size, spatial
structure, surface structure and defects, which are strongly related to its
photocatalytic performance. Therefore, all of these mentioned factors
can be considered self-modification.
Among different self-modification methods, molecular structure
regulation, defects engineering and micro morphology design are the
most widely adopt. Molecular structure design and adjustment can
regulate the electronic band structure of g-C3N4 and thus change the
generation, separation and utilization of charge carriers. In addition,
defects usually arise from the breakage and disruption of the perfect
basic units, which change the chemical sluggishness of intrinsic graphite
p-conjugated structure and are expected to decrease the recombination
of charge carriers. At the same time, micro morphology design, is
commonly used in changing the specific surface area and the exposure of
the active site, as well as changing the charge transfer distance during
the photocatalytic process. All of these strategies are efficient in
improving the PHE ability of pristine g-C3N4.
6.1. Molecular structure regulation
As mentioned above, the graphene like π-π conjugate structure of g-
C3N4 is considered to be the origin of the photocatalytic activity [12,86].
Based on this fact, it is believed that the photocatalytic performance of g-
C3N4 can be adjusted through interfering the charge transfer in the
π-conjugate system [87–94]. By adjusting the chemical composition and
local structure of g-C3N4 at molecular level, the electronic band struc­
ture of g-C3N4 can be effectively regulated, so as to the light absorption
capacity, photocurrent characteristics and the charge separation effi­
ciency, and thus improving the photocatalytic activity of g-C3N4
essentially.
6.1.1. Molecular doping
From the point of adjusting the π-π conjugate, the most commonly
D. Ma et al.
adopt strategy is molecular doping, that is, the co-polymerization of g-
C3N4. Through introducing other structure-matching small molecules
during the copolymerization process, the target monomers with
different chemical compositions can be embedded into the conjugated
structure of g-C3N4 through chemical bonding, so as to regulate the
electronic band structure, improve the light absorption capacity and
promote the separation of photogenerated carriers [88,91,94].
The earliest copolymerization of g-C3N4 was reported by Zhang et al.
[95] through the Schiff-based reaction between barbituric acid and
dicyandiamide. As shown in Fig. 11a, the added barbituric acid can be
directly incorporated into the classical structure of g-C3N4 during the
high temperature treatment, and the obtained samples displayed
remarkable redshift of optical absorption from 470 to 750 nm when the
addition amount of barbituric acid gradually increased (Fig. 11b). The
red-shift of light absorption edge mainly comes from the decreased band
gap caused by the introduction of barbituric acid (Fig. 11c), which can
be ascribed to the efficiently expanded π-π conjugate due to the co-
polymerization of g-C3N4, and thus resulting in an obviously increased
hydrogen evolution activity, 5 times higher than that of original g-C3N4.
Fig. 11. (a) Proposed copolymerization processes of dicyandiamide with barbituric acid at high temperature, (b) UV/Vis diffuse-reflectance spectra of g-C3N4 and
barbituric acid copolymized g-C3N4 samples, (c) Mott-Schottky plots and band structure of g-C3N4 and barbituric acid copolymized g-C3N4 samples. Adapted with
permission from ref [95]. Copyright 2010 Wiley-VCH.
10
Coordination Chemistry Reviews 500 (2024) 215489
Zhou et al. [96] constructed the carbon ring and stereo molecular
scaffold co-doped g-C3N4 NSs (AGCN). It was found that the introduc­
tion of carbon ring changed the in-plane connection of g-C3N4 through
the sp2-hybridized C-N bonds, which extended the delocalization of π
electrons and facilitated the exfoliation of bulk g-C3N4 (Fig. 12a). The
synergistic effect of the above two aspects resulted in 12.9 times of H2
evolution ability (Fig. 12b).
Jiao et al. [97] fabricated the nitrobenzene inarched g-C3N4 nano­
tube photocatalyst (CN-DNP) by using a copolymerization method. The
aromatic ring in nitrobenzene grafted into the triazine ring of g-C3N4
(Fig. 13a), thus enhancing the conjugation of g-C3N4 and promoting
electron delocalization. The introduction of nitro group enabled pho­
togenerated electrons to transfer from the center to the both ends of g-
C3N4 nanotube and facilitated the separation of photogenerated elec­
trons and holes. At the same time, the introduction of nitrobenzene
narrowed the bandgap of CN from 2.7 eV to 2.5 eV (Fig. 13b) and
resulted in 11.2 folds higher H2 evolution ability than CN (Fig. 13c). This
work clarified the possibility of introducing extra group on the edge of g-
C3N4 through the molecular doping to promote the separation of charge
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 12. (a)Schematic illustration of the charge transfers and separation on the AGCN skeleton under visible light. (b) the visible light PHE rate (λ > 420 nm) of the
samples. Adapted with permission from ref [96]. Copyright 2021 Elsevier.

Fig. 13. (a) the possible polymerization schematic illustration of CN-DNP formation, (b) band structure of the CN and CN-DNP0.1 samples, (c) photocatalytic
hydrogen activity of photocatalysts in visible light (λ＞420 nm), (d) proposed photocatalytic mechanism for hydrogen production over CN-DNP under visible light
irradiation. Adapted with permission from ref [97]. Copyright 2022 Elsevier.

carriers on spatial to accelerate the utilization of electrons and the
generation of H2 (Fig. 13d).
Based on the co-polymerization strategy, some other precursors,
including pyridine, thiophene, benzene ring, diaminomaleonitrile, etc.,
have also been utilized as molecular modification monomer by re­
searchers. In these systems, the intrinsic framework of g-C3N4 is broken
by the new anchored group, thus changing the delocalization of the π
electrons and optimizing the π-conjugated systems, and the obtained
molecular-modified samples display much improved H2 evolution abil­
ity than the unmodified g-C3N4 [98–100].
6.1.2. Ion doping
Different from molecular doping, ion doping is a way of modifying
the electronic structure of g-C3N4 by introducing impurity ions. Ion
doping usually results in lattice defects, which changes the electronic
band structure of g-C3N4, thus adjusting the light absorption perfor­
mance, separation and utilization efficiency of charge carriers, and ul­
timately improving the photocatalytic activity of g-C3N4. The commonly
studied ion-doped g-C3N4 photocatalysts and their corresponding PHE
performance in recent years are summarized in Table 2.
According to the nature property of impurity ions, ion doping
including metal ion doping and non-metal ion doping. In ion doping, the
introduced metal ions usually introduce new impurity levels into g-
C3N4, which broadens the absorption spectrum of the system or inhibits
the recombination of photogenerated electron-hole pairs. The typically
studied ion doping systems, such as alkali earth metal elements (sodium,
potassium) and transition metal elements (iron, copper, cobalt and
molybdenum), have been proven to be efficient in improving the PHE of

11
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Table 2
The commonly studied ion doped g-C3N4 in recently few years and the PHE activities of corresponding photocatalysts.
catalyst mass of catalyst Reaction solution Co- Light source R (H2) (μmol/ R (H2) of pure g-C3N4 Ref. (year)
(mg) catalyst g/h) (μmol/g/h)

B-g-C3N4 10 80 mL H2O and 20 mL TEOA 3 wt% Pt 300 W Xe lamp, 1639.39 901.35 [119]
>400 nm (2022)
3 3
B-g-C3N4 40 40 mL H2O and 20 mL methanol 1 wt% Pt Xe lamp, 350–700 3.80 × 10 2.25 × 10 [118]
nm (2021)
C-g-C3N4 20 40 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp, 1266.8 732.5 [107]
>420 nm (2020)
C-g-C3N4 100 180 mL H2O and 20 mL methanol 1 wt% Pt 500 W Xe lamp 216.8 75.8 [112]
(2019)
3
O-g-C3N4 25 90 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp, 2.2 × 10 0.68 × 103 [134]
>420 nm (2020)
P-g-C3N4 10 90 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp 6437 458 [135]
(2020)
P-g-C3N4 10 80 mL H2O and 20 mL TEOA 3 wt% Pt 300 W Xe lamp, 2.96 × 103 1.01 × 103 [116]
>400 nm (2021)
P-g-C3N4 50 72 mL H2O and 8 mL TEOA 3 wt% Pt 300 W Xe lamp, 10.985 1.445 [202]
>420 nm (2022)
Co-g-C3N4 20 40 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lam 3485.17 1161.17 [101]
(2019)
Co-g-C3N4 50 90 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp, 808.92 252.6 [106]
>420 nm (2021)
Co-g-C3N4 80 50 mL H2O and 6 mL TEOA 3 wt% Pt 300 W Xe lamp, 6227 803.6 [125]
>400 nm (2018)
K-g-C3N4 30 40 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp, 919.5 70.4 [105]
>420 nm (2019)
K-g-C3N4 30 90 mL H2O and 10 mL TEOA and 3 wt% Pt 300 W Xe lamp, 4.84 × 103 0.09 × 103 [127]
1 g NaCl >420 nm (2020)
S/K-g-C3N4 30 90 mL H2O and 10 mL TEOA and 3 wt% Pt 300 W Xe lamp, 8.78 × 103 0.09 × 103 [127]
1 g NaCl >420 nm (2020)
O/W-g- 50 80 mL H2O and 20 mL TEOA 1 wt% Pt 300 W Xe lamp, 403.57 171.21 [126]
C3N4 >400 nm (2021)
Mo/S-g- 25 90 mL H2O and 10 mL methanol N/A 300 W Xe lamp, 294 0 [123]
C3N4 >420 nm (2021)
Y/S-g-C3N4 10 27.9 mL H2O and 2.1 mL TEOA 1 wt% Pt 500 W Xe lamp, 19.2 1.2 [128]
>420 nm (2021)
C/O-g- 10 90 mL H2O and 10 mL TEOA 3 wt% Pt 300 W Xe lamp, 562 93 [130]
C3N4 >420 nm (2020)
Na/O-g- 50 60 mL H2O and 20 mL ethanol 1 wt% Pt 300 W Xe lamp, 110 16 [124]
C3N4 >400 nm (2017)

pure g-C3N4 [101–110]. Metal ions doping can be achieved by a simple
method in which metal salts, C precursors and N precursors are calcined
together. Jiang et al. [101] carried out a comprehensive study of alkali
metal-doped g-C3N4. As shown in Fig. 14a and b, the declined signals in
the XRD and BET measurements were observed when the doping atom
changed from C, Li, Na, to K. The XRD signal at 27.4◦ can be ascribed to
the interplanar stacking of g-C3N4, and the intensity of this peak grad­
ually weakened with the doping atom changing from C, Li, Na, to K,
implying that the in-plane structure was partially fragmented into
smaller crystallites. In addition, the decline specific surface area came
from the destruction and collapse of the pore structure caused by the
used basic reagents. It was found from Fig. 14c that the dopant of alkali
metals results in narrower band gaps with more positive VB and less
negative CB positions, indicating more efficient visible light utilization
and charge excitation efficiency. As a result, the doped samples with
alkali metals displayed much higher H2 evolution ability than pure g-
C3N4 (Fig. 14d), demonstrating that the metal ion doping is efficient in
improving the photocatalytic activity of g-C3N4.
Hu et al. [107] synthesized a series of K-doped g-C3N4 by co-
calcination of potassium hydroxide and dicyandiamide, and studied
the effect of K dopant amount on the energy band stricture of g-C3N4. It
was found that the introduction of K atom resulted in a series of
adjustable energy band structure of g-C3N4 (Fig. 15), and the proper
band structure makes it possible to produce both ⋅OH and ⋅O2− radicals
at the same time, thus effectively promoting the photocatalytic activity
of g-C3N4. Wang et al. [108] doped Mo ions in flower-like g-C3N4
through the combination of hydrothermal method and calcined method,
and found that the introduction of Mo reduces the band gap width of g-
C3N4 from 2.74 to 2.56 eV, and enlarges the corresponding light ab­
sorption range. In addition, the introduced impurity ion inhibits the
recombination of photogenerated electron-hole pairs, thus significantly
increasing its PHE activity. Sun et al. [109] reported that the treatment
of g-C3N4 with KOH can achieve the simultaneous K-doping and exfo­
liation of g-C3N4, which endows the g-C3N4 with high surface area,
enlarged conductive band edge, promoted charge generation and sepa­
ration as well as the long life-time of photogenerated carriers.
Using the coordination effect between Pd and g-C3N4, Wang et al.
[104] fabricated the palladium-doped graphitic carbon nitride (g-C3N4-
Pd) photocatalyst through a calcination method (Fig. 16a), and the
successful dopant of Pd atom can be confirmed from the element map­
ping (Fig. 16b). In XRD measurement, g-C3N4-Pd displayed a shift of the
(1 0 0) peak toward low angle (Fig. 16c and d), indicating that the
introduction of Pd atom leads to the increase of the distance of in-planar
nitride pores. At the same time, no shift was observed over the peak at
around 27.4◦ corresponding to the interlayer distance of g-C3N4, indi­
cating that the Pd atoms locate at the sixfold cavities of g-C3N4. In
addition, due to the existence of Pd atoms, the light absorption edge of g-
C3N4 was extended toward longer wavelength (Fig. 16e), which is
benefit to the photocatalytic reaction. The g-C3N4-Pd20 displayed the
highest photocatalytic H2 evolution activity of 316.2 μmol/g in 3 h
(Fig. 16f), which is 15.3 times higher than that of pure g-C3N4. Based on
the theoretical calculation, the Gibbs free energy of hydrogen adsorbed
on Pd is greatly reduced to − 1.82 eV compared with hydrogen adsorbed
on g-C3N4 (− 3.71 eV) (Fig. 16g), indicating that the Pd doping improves
the hydrogen evolution kinetics on g-C3N4. Thus, it can be concluded
that the introduction of Pd atoms harvests photogenerated electrons

12
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 14. (a) XRD signal intensity, (b) BST measurements, (c) band structures and (d) hydrogen evolution rates for pristine g-C3N4 and modified g-C3N4. Adapted with
permission from ref [101]. Copyright 2017 Elsevier.

Fig. 15. (a) UV–vis diffuse reflectance spectra of as-prepared g-C3N4-based catalysts, inset is the possible doping site for K ions in K(x)–CN, (b) band gap structures of
as-prepared g-C3N4 and K(x)–CN. Adapted with permission from ref [107]. Copyright by 2015 Royal Society of Chemistry.

from g-C3N4 and plays the role of active sites for hydrogen evolution
(Fig. 16h). This work demonstrates that the doping of metal ions not
only plays the role of band structure manipulation, but also works as
reaction active sites to facilitate the generation of hydrogen.
Although much efforts have been made in the research of metal ion
doped g-C3N4, some headache problems, such as high cost,
contamination of metal element, and poor thermal stability, are still
cannot be ignored. The introduction of non-metallic elements has
attracted increasing research interest these years. Compared to metal
ions, the band structure of g-C3N4 can be regulated by doping non-
metallic elements without changing its non-metallic properties. Up to
now, nonmetallic elements including C, N, O, phosphorus (P), sulfur (S),

13
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 16. (a) Schematic of the synthesis of g-C3N4-Pd photocatalysts, (b) HAADF-STEM image of g-C3N4-Pd20 and elemental maps of C, N, and Pd, (c) full XRD
patterns of g-C3N4 and Pd-doped g-C3N4 samples, (d) enlarged XRD view of (1 0 0) peaks, (e) intensity ratios of (0 0 2) to (1 0 0) peaks of the four samples, (f) ab­
sorption spectra of g-C3N4 and differently Pd-doped g-C3N4 samples. The inset is the photographs of the samples, (g) hydrogen produced ability within 3 h for the four
samples, (h) free-energy diagram of H adsorbed on g-C3N4 and Pd-doped g-C3N4, (i) mechanism of PHE in Pd doped g-C3N4. Adapted with permission from ref [104].
Copyright 2018 American Chemical Society.

Fig. 17. (a) Synthesis procedure of porous PCN-S, (b) top and side view of the optimized pure g-C3N4 and P-doped g-C3N4 configuration, color scheme: C, grey; N,
blue; P, orange, (c) electronic band structures of CN-B, CN-S, PCN-B, and PCN-S. (d) photocatalytic H2-production mechanism of porous PCN-S. Adapted with
permission from ref [125]. Copyright 2015 Royal Society of Chemistry.

14
D. Ma et al.
boron (B) and halogen have been introduced into the structure of g-C3N4
and have been proven to be effective in obtaining much improved
photocatalytic activity [111–126]. For example, Ran et al. [125] fabri­
cated P atom doped g-C3N4 NSs (PCN-S) through a combination of P
doping and the thermal exfoliation method (Fig. 17a). All the doped P
atoms replace C1 in the heptazine unit of PCN-S, which enlarges the in-
planar distance of nitride pores from 6.95 Å to 7.04 Å (Fig. 17b). At the
same time, the doped P atoms bring mid-gap states into g-C3N4, which
plays the role of electron capture center to harvest photogenerated
electrons from g-C3N4, thus efficiently improving the separation and
transport efficiency of photogenerated carriers (Fig. 17c and d).
In 2021, Zhao et al. [127] fabricated boron atom doped g-C3N4 NSs
(BDCNN) via a two-step ultrasonication-calcination process (Fig. 18a)
by using NaBH4 as the B-precursor. It was found that the introduced B
atom brings a mid-gap state into the forbidden band of g-C3N4, which
results in a red-shift of the light absorption edge and a changed color
from pale yellow to dark brown (Fig. 18b and c). The energy band shift
induced by B atom can be confirmed from the overall water splitting
reaction (Fig. 18d and e), in which the compound of BDCNN and CNN
are capable in generation of O2 and H2 at the same time and keep stable
in long time recycle. This is because that both the VB and CB positions of
the BDCNN are much lower than that of CNN (Fig. 18c), the band energy
position shifted much downward enables BDCNN to drive the water-
oxidation reaction while the CB of CNN is negative enough for H2
reduction reaction.
In recent years, the fabrication of dual-element doped g-C3N4 system
has attracted more and more attention [113,127–133]. Li et al. [127]
Fig. 18. (a) Schematic of the synthesis of BDCNN derived from CNN, below are respectively the TEM images of CNN and BDCNN, (b) UV–visible DRS of CNN and
BDCNN, insets show photographs of the CNN and BDCNN, (c) band structure alignments for CNN and BDCNN, (d) the overall water-splitting performance and (e)
cycling of photocatalytic overall water splitting over CNN/BDCNN. Adapted with permission from ref [126]. Copyright 2021 Springer Nature.
15
Coordination Chemistry Reviews 500 (2024) 215489
fabricated Mo/S co-doped porous g-C3N4. Fang and coworkers [128]
fabricated the Na/O co-doped g-C3N4. Si et al. [129] reported the Co/N
co-doped g-C3N4. Wei et al. [130] reported the fabrication of W/O co-
doped hollow g-C3N4 tubular structure, which displayed 2.5 times
higher H2 evolution activity than pure g-C3N4. Chen et al. [131] re­
ported that the S/K-co-doped g-C3N4 displayed 98 times higher H2
evolution rate than the pristine g-C3N4. All of these results have
demonstrated that the synergistic effect in the co-doped g-C3N4 is more
benefit to the expanding of light absorption region, the exposure of
specific surface area and active reaction sites, the separation of charge
carriers, as well as the optimization of photoreduction potential. The
fabrication of double element doped g-C3N4 may provide an alternative
for the development of high-performance g-C3N4 with a cost-effective
and facile path.
Molecular structure regulation is an easy operated path in improving
the photocatalytic active of g-C3N4, both metal/non-metal elements and
the functional groups can be introduced into g-C3N4 through a simple
thermally polymerizing or copolymerizing method by reacting with the
precursors containing target elements, the ultimate aim of molecular
structure regulation is to manipulate the band structure of g-C3N4
through shrinking the band gap, improving the CB potential or creating
doped energy level, which is benefit to expand the light absorption
wavelength, increase the reducibility of photogenerated electrons and
suppress charge recombination.
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

6.2. Defect engineering
Except for the introduce of impurity atoms, the photocatalytic per­
formance of g-C3N4 can also be regulated through constructing nitrogen
or carbon defects into the heptadazine structure unit. This is to say,
breaking the intrinsic π-π conjugate of pristine g-C3N4 [53,136–141]. As
a matter of fact, defects are essential for photocatalytic reactions
because they can provide active sites for reaction and are efficient in
expanding the visible light absorption range of the material by intro­
ducing additional energy bands into the forbidden band of g-C3N4. At the
same time, the existence of defects usually serves as trapping sites to
suppress the recombination of electron-hole pairs, thus to improve the
utilization of photogenerated charge carriers [142–148].
Compared with the doping strategy, defect engineering is a self-
modification strategy of molecular structure without introducing im­
purities, which is more beneficial to the long-time durability of the
photocatalysts. For example, Liang et al. [139] treated bulk g-C3N4 at
the temperature of 490–520 ℃ under ammonia (NH3) atmosphere, and
the obtained g-C3N4 NSs displayed sufficient carbon vacancies, which
extended the light absorption edge to near-infrared region and brought
nearly 20 times enhanced photocatalytic hydrogen production capacity
than that of before-treated g-C3N4. Objectively speaking, this strategy
asks for a relative harsh reaction condition and usually results in uneven
surface defects. Later, Yu et al. [140] reported the fabrication of nitrogen
defect rich g-C3N4 NSs by using an alkali assisted method, which effi­
ciently avoids the high temperature treatment process in reducing at­
mosphere and can facilitate the formation of uniform phase defects at
the same time. The obtained sample displayed superior visible light
absorption capacity and photogenerated electron-hole separation effi­
ciency, as well as the greatly improved photocatalytic performance. Niu
et al. [53] created nitrogen vacancies by treating g-C3N4 in a H2 atmo­
sphere at the temperature of 520 to 550 ◦ C. As shown in Fig. 19a,
compared with the material without layered structure, the layered
structure property of g-C3N4 enabled H2 to easily penetrate the layer gap
of carbon nitride through diffusion and enter the inner of bulk g-C3N4,
thus formed a homogeneous self-modification with vacancies. Based on
the DFT calculations (Fig. 19b and c), the formation of vacancies is due
to that a N atom at the position of N2 was reduced into NH3 molecule
because of the lowest change in energy (ΔE) of 0.65 eV, thus induced a
nitrogen vacancy in the Triazine ring skeleton of g-C3N4. It was noticed
from the UV–vis absorption spectra that the H2 treated sample displayed
much enlarged light absorption ability in the visible region (Fig. 19d),
this is because that the formation of nitrogen vacancy reduced the direct
band gap of g-C3N4 from 2.34 eV to 1.70 eV as a result of down-shifted
CB and up-shifted VB edges (Fig. 19e and f). It is confirmed that, the
introduction of vacancies contributes to the expanded light absorption
capacity due to the formation of intermediate energy level. However, it
should be emphasized that, this expansion of light absorption ability

Fig. 19. (a) Schematic illustration of difference of H2 reduction results in the nonlayered material and the layered material, (b) g-C3N4 and (c) H2 reduced g-C3N4
with one group of NH2 (located at N2) substituted by a H atom. (d) UV–visible absorption spectra of the samples, (e) Band structures calculation of g-C3N4 and H2
reduced g-C3N4, (f) VB and CB positions of g-C3N4 and H2 reduced g-C3N4. Adapted with permission from ref [53]. Copyright 2014 Wiley-VCH.

16
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

comes at the expend of the reduction of REDOX capacity of photo­
generated charge carriers, which may have adverse effects on photo­
catalysis because too low REDOX potential would unable to overcome
the energy barrier required for hydrogen production.
Huang et al. [144] treated g-C3N4 with nitric acid to introduce N
vacancies into the sample. It was found that the N vacancies might be
replaced by O atoms, thereby adjusting the visible light absorption, band
gap, carrier density as well as the separation efficiency of photo­
generated charge carriers. Moreover, based on the intrinsic relationships
between the surface functionalities and PHE rates, it was concluded that
the -O-H species in CNx act as an inhibitor for H2 production, while the
–C=O/-O, -NHx and N defects at N2C sites (including N vacancies and N
replaced by O atoms) act as the active sites for the generation of
hydrogen (Fig. 20a). As a result, the decoration of N vacancies improved
the photocatalytic H2 evolution to as high as 1160 μmol/h/g, which was
about 19 times higher than that of pristine g-C3N4 (Fig. 20b). Yang et al.
[147] induced heterogeneous structural defects in porous g-C3N4
through a facile treatment method, in which the edge nitrogen and
cyano group were replaced by oxygen atom. The formation of C-NHx
bonds on the edge of aromatic ring, the reduced electron density of ni­
trogen atoms, as well as the formation of N-C-O and C=O species in the
lattice can be confirmed from the XPS measurements (Fig. 20c to e), it
thus can be concluded that cyano group trends to appear at apex of
melon structure following the de-protonation of C-NHx species
(Fig. 20f). Consequently, the after modified sample displayed a high H2
evolution performance of with an AQE of 8.41 % at the wavelength of
420 nm (Fig. 20g to i). This can be ascribed to the results based on
theoretical calculation that the doped oxygen atom and the nearby
atoms accept electrons as reduction site to produce hydrogen, while the
un-doped fraction and cyano group take the duty to oxidize water. Their
works demonstrated that the proper defect engineering can facilitate the
separation and utilization of charge carriers in space and thus acceler­
ating the generation of hydrogen.
In general, the distribution and type of defects have direct effect on
the PHE active of g-C3N4. The formation of defect can be manipulated
through the fabrication strategy and the addition of strong acid or
alkaline liquid, which usually introduced strongly electronegative
functional groups, such as -OH, -COOH, -OCH3 and -NHx and result in a
change of local electronegativity and thus facilitating the separation of
charge carriers. Compared with molecular structure regulation strategy,
defect engineering can not only affect the electronic distribution and
energy band of g-C3N4, but also change the reaction dynamics of PHE by
increasing the exposure of active reaction surface, facilitating the
adsorption and desorption process of intermediate H*, as well as
changing the local electron distribution in g-C3N4 molecule to improve
charge separation efficiency. Both the introduction of impurity elements
and the defects engineering focus on expanding the light response,
changing local electron density, as well as manipulating the energy band
structure, which is expected to accelerate the generation, separation and
utilization of charge carriers. Nonetheless, it should be mentioned that
the introduction of doping elements and defects also suffered the for­
mation of new charge recombination traps in the g-C3N4 sometimes,
which result in the decline of PHE active. Therefore, careful selection of
preparation methods and optimization of the concentration and distri­
bution of dopants and defects is required to minimize negative effects.

Fig. 20. (a)The active-site structure diagram of CNx for photocatalytic H2 production, (b) time course of H2 evolution for CN0 and CN3. Adapted with permission
from ref [144]. Copyright 2019 Elsevier. (c) to (e) are the high resolution XPS spectra of (c) C1s, (d) N1s and (e) O1s for GCN and COC30, (f) charge density difference
comparison after loading oxygen atom and cyano group, (g) photocatalytic generated hydrogen amount of GCN and COC30, (h) Hydrogen amount of GCN and COC30
under monochromatic light illumination with the corresponding AQEs in the inset figure, (i) the cycling PHE of GCN and COC30 for 40 h. Adapted with permission
from ref [147]. Copyright 2019 Elsevier.

17
D. Ma et al.
6.3. Optimization of microstructure
Microstructure optimization is another important method in
improving the photocatalytic performance of g-C3N4. From the micro­
scopic point of view, the structure regulation of g-C3N4 mainly includes
multi-dimensional design and the introduction of porous structures,
which is to increase the specific surface area and increase the reactive
active sites.
6.3.1. Design and construction of multi-dimensional nanostructures
The photocatalytic performance of g-C3N4 can be controlled through
the size distribution and morphology characterization. Up to now, the
typical nanostructure g-C3N4 include zero-dimension (0D) quantum
dots, one-dimensional (1D) nanowires, nanotubes and nanorods, two-
dimensional (2D) NSs, three-dimensional (3D) nanoflowers and nano­
network structures have been studied. Multi-dimensional structure
design endows g-C3N4 with different physical and chemical properties,
thus making the generation and utilization of charge carrier adjustable
and expanding the regulatory scale of photocatalytic performance.
6.3.1.1. 0D nanostructure g-C3N4. 0D nanostructure g-C3N4 is usually
the quantum dots with a tiny size of 1 ~ 10 nm, the most outstanding
merit is the sufficient surface-active sites due to the large relative surface
area. In addition, the tiny size of 0D g-C3N4 makes it easy to be combined
with other materials or loaded into some materials with special struc­
ture. At the same time, it was reported that the 0D g-C3N4 often displays
special light absorption ability and optical emission to that of bulk phase
materials due to the quantum size effect, and thus have attracted much
researches [149–152]. 0D g-C3N4 can be prepared by the “bottom-up”
methods such as low temperature solid phase strategy and microwave
assisted strategy, as well as the “top-down” methods through thermo­
chemical or electrochemical etching of bulk g-C3N4. Zheng et al. [153]
fabricated the g-C3N4 quantum dots with the size of about 3.2 nm by
using a thermal chemical etching method. Compared with bulk material,
the obtained 0D g-C3N4 efficiently shorten the transport path of charge
carriers and improved the separation of photogenerated electron-hole
pairs. Wang et al. [152] fabricated 0D g-C3N4 quantum dots from bulk
Fig. 21. (a) Schematic illustration of the controllable synthesis of g-C3N4 NSs, nanoribbons and quantum dots, (b) TEM images and (c) diameter distribution of
CNQDs, (d) PL spectra of the CNQDs at different excitation wavelengths. Inset: photograph of the CNQD aqueous solution taken under 365 nm UV light, (e) the up-
conversion PL spectra of the CNQDs, (f) photocatalytic H2 production for the samples with 1 wt% Pt under visible light irradiation (λ > 420 nm) using trietha­
nolamine as the sacrificial agent, (g) Proposed photocatalytic mechanism for CNQDs under visible light. Adapted with permission from ref [152]. Copyright 2014
Royal Society of Chemistry.
18
Coordination Chemistry Reviews 500 (2024) 215489
g-C3N4 directly by using a thermal-chemical etching process (Fig. 21a),
the obtained g-C3N4 quantum dots have a small size distribution of 5 ~
9 nm (Fig. 21b and c). Due to the special quantum size effect, the sample
displayed excitation-wavelength-depended photo luminescence under
the wavelength from 340 to 420 nm (Fig. 21d). Importantly, they
observed obvious up-conversion luminescence properties over the
CNQDs (Fig. 21e) for the first time. The special up-conversion PL
properties indicates that the CNQDs can convert NIR light to visible light
and makes it possible in take use of the solar energy at NIR region to
accelerate the photocatalytic reaction. As shown in Fig. 21f, when
combined with bulk g-C3N4, the as-fabricated sample displayed much
increased H2 evolution ability. Upon photo-excitation (Fig. 21g), visible
light with wavelength shorter than 600 nm can be harvest by the bulk g-
C3N4 while the long wavelength (＞600 nm) is upconverted by CNQDs
for the subsequent excitation of g-C3N4 to form electron-hole pairs. As a
result, CNQDs show promise to be used as general energy-transfer
components in photo catalytic systems to harness the Vis-NIR spec­
trum of sunlight.
6.3.1.2. 1D nanostructures g-C3N4. Compared to 0D materials, 1D
nanostructures can provide fast conduction channels for photogenerated
charge transport, at the same time, the physical and chemical properties
of materials can be optimized by adjusting the length and diameter of
the material, thus improving their photocatalytic performance. In recent
years, 1D g-C3N4 such as nanowires, nanorods, nanotubes and nano­
ribbons have been reported and proven to be more efficient in photo­
catalysis than that of bulk materials [139,153–160]. You et al. [159]
fabricated the g-C3N4 through the template-free thermal condensed
process. Li et al. [162] reported the fabrication of 1D tubular g-C3N4 by
using a modified chemical method. Zeng et al. [156] fabricated the 1D
porous g-C3N4 by direct calcination method (Fig. 22a to c). Zhang et al.
[160] fabricated helical g-C3N4 nanorods with left-handed and right-
handed chirality by using mesoporous silica as template. The chiral g-
C3N4 nanorods exhibited unique optical properties for circular-polarized
light at the optical absorption edge and efficiently enhanced the charge
carrier mobility due to the special rod-like structure, which thus wit­
nessed an improved photocatalytic performance. Liu et al. [161]
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 22. (a) schematic illustration of the formation of g-C3N4 nanorod/InVO4 hollow sphere composites. Adapted with permission from ref [159]. Copyright 2017
Elsevier. (b) schematic illustration of the synthesis of the core–shell LaPO4/tCN nanocomposites. Adapted with permission from ref [162]. Copyright 2017 Elsevier.
(c) Synthesis procedure of porous O-g-C3N4 NR. Adapted with permission from ref [156]. Copyright 2017 Elsevier.

prepared P-doped g-C3N4 nanotubes with a diameter of about 200 nm by significantly reduced impedance to photogenerated carriers and excel­
co-calcination of sodium hypophite and melamine in a one-step method. lent photocatalytic performance.
Compared with bulk g-C3N4, P-g-C3N4 nanotubes displayed a Bai et al. [158] achieved the conversion of g-C3N4 from 2D

Fig. 23. (a) The Schematic illustration of the formation process of g-C3N4 nanorods from g-C3N4 nanoplates, (b) Photo-responses of g-C3N4 nanoplate and g-C3N4
nanorod electrodes under visible light irradiation (λ > 420 nm, [Na2SO4] = 0.1 M). Apparent photocatalytic performance over g-C3N4 nanoplates and g-C3N4
nanorods: (c) under visible light (λ > 420 nm) and (d) under simulated solar (λ > 290 nm). Adapted with permission from ref [158]. Copyright 2013 American
Chemical Society.

19
D. Ma et al.
nanoplates to 1D nanorods by using a simple reflux method (Fig. 23a),
the as-fabricated 1D g-C3N4 nanorods displayed much higher photo­
catalytic activity and photocurrent intensity than that of g-C3N4 nano­
plates under visible light (Fig. 22b to d).
Zeng et al. [156] fabricated 1D porous architectural g-C3N4 nanorods
(NRs) through the calcination of hydrous melamine nanofibers
(Fig. 24a). The formation g-C3N4 NRs with porous structure can be
confirmed from the morphology characters including TEM and SEM
images in Fig. 24b and c. The thermal treatment brings O impurity into
g-C3N4 and forms the oxygen-doped g-C3N4 structure (Fig. 24d). It was
noticed that the O doped g-C3N4 NRs shrunk the light absorption ability
of bulk g-C3N4 (Fig. 24e) and changed the VB position from +1.68 for
bulk g-C3N4 to +1.85 eV (Fig. 24f and g). Although O-g-C3N4 NRs dis­
played weaker light absorption ability than that of bulk g-C3N4, the H2
evolution ability of O-g-C3N4 NRs was much higher than the later sample
(Fig. 24h). Compared to bulk g-C3N4, the porous 1D nanorods provide
more specific surface area for photocatalytic reaction and the porosity of
the material provides large number of active sites and quick access to
reactants. Compared with bulk materials, the 1D nanorods have larger
specific surface area and more sufficient surface-active sites, as well as
the accelerated interfacial movement of photogenerated electrons along
the length of rods, thus dramatically accelerated the axial charge
transfer and improved photocatalytic performance [163].
6.3.1.3. 2D nanostructures g-C3N4. The fabrication of 2D g-C3N4 nano­
structure is one of the research hotspots of two-dimensional layered
materials, and has have been widely studied in PHE [136,164–180]. g-
C3N4 is a graphene like layer structure, but the strong interlayer van der
Waals force usually induces the harmful interlayer stack and results in a
low specific surface area (even less than 10 m2/g), at the same time, the
charge carriers recombination in the bulk material is also an adverse
Fig. 24. (a) Schematic illustration of O-g-C3N4 NR formation: morphologies (top) and structures (bottom), (b) TEM image of O-g-C3N4 NRs, (c) SEM image of O-g-
C3N4 NRs, (d) HADDF, EDS and element mapping of O-g-C3N4 NRs with the addition of 3 wt% Pt. Adapted with permission from ref [156]. Copyright 2017 Elsevier.
20
Coordination Chemistry Reviews 500 (2024) 215489
factor in PHE [167–172]. As an unique 2D photocatalyst, g-C3N4 NSs
retain the original aromatic heterocycle structure of the C-N compound,
which contributes to the high speed in plane transfer of electrons due to
the π-π conjugate. At the same time, the 2D structure significantly
shorten the charge transfer distance from inner to the surface of pho­
tocatalyst compare to that of bulk materials. Moreover, similar to 0D
quantum dots, 2D NSs also provides abundant active sites, which is
conducive to the light harvest and the adsorption of reactant molecules
[171–173,180]. Up to now, both monolayer and multilayer g-C3N4 NSs
have been successfully prepared and reported. Some researchers ob­
tained g-C3N4 NSs through peeling from bulk material by using physical
or chemical methods, and others fabricated g-C3N4 NSs through the
utilization of suitable two-dimensional templates (Fig. 25). For example,
Liang et al. [164] fabricated single-layer g-C3N4 NSs through peeling
bulk g-C3N4 under the assist of ultrasonic in the pure water medium, the
obtained single-layer g-C3N4 NS was about 55 nm in the transverse
dimension and 0.6 nm in thickness, and the production yield of the
sample was about 30 %. Importantly, the sample displayed much higher
visible light driven catalytic activity than that of multilayer g-C3N4 NSs.
Fan et al. [180] fabricated g-C3N4 NSs by using diatom matrix as tem­
plate, and the obtained g-C3N4 NSs displayed large specific surface area
(135 m2/g) and better electron hole pair separation characteristics,
which resulted in a significantly improved visible light catalytic ability
than that of bulk sample.
Qu and co-workers [170] synthesized a single atomic layered g-C3N4
mesh through the solve-thermal exfoliation of mesoporous g-C3N4
(Fig. 26a), the g-C3N4 mesh displayed a thin thickness of less than 0.5
nm (Fig. 26b and c). The as fabricated g-C3N4 mesh displayed an up­
ward shifted energy band compared with that of bulk g-C3N4, indicating
an improved reduction ability of the photogenerated electrons. As a
result, the H2 evolution rate of the monolayer mesoporous g-C3N4 mesh
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 25. The fabrication of two dimension by g-C3N4 using different strategies (a) bath and probe sonication strategy. Adapted with permission from ref [164].
Copyright 2017 Science China Press and Springer-Verlag Berlin Heidelberg. (b) thermal exfoliation strategy. Adapted with permission from ref [172]. Copyright 2020
Elsevier. (c) liquid exfoliation strategy. Adapted with permission from ref [174]. Copyright 2020 Elsevier. (d) and (e) are calcination method. Adapted with
permission from ref [166], copyright 2016 Wiley-VCH and adapted with permission from ref [136], copyright of 2020 Elsevier. (f) chemical exfoliation strategy.
Adapted with permission from ref [57]. Copyright 2013 Royal Society of Chemistry. (g) and (h) are TEM images of two-dimension g-C3N4. Adapted with permission
from ref [173]. Copyright 2016 Elsevier.

Fig. 26. (a) Fabrication process of monolayer mesoporous g-C3N4 NSs. (b) AFM image of the synthesized mesoporous g-C3N4NSs; the inset shows the enlarged view
of the rectangle area. (c) height profiles along the lines in (b). (d) the valence band spectra and electronic band structure of the monolayer mesoporous g-C3N4 NSs
and the bulk counterpart. (e) photocatalytic activity of (i) the monolayer mesoporous g-C3N4 nanomesh, (ii) the bulk counterpart, (iii) the traditional g-C3N4 bulk
under irradiation with visible light (＞420 nm). Adapted with permission from ref [170]. Copyright 2016 American Chemical Society.

21
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

was measured to be 8510 μmol/h/g, which was much higher than that
over other 2D g-C3N4 nano structures reported previously. Nowadays,
there is still plenty of room for us to increase its specific surface area
because its theoretical specific surface area can reach 2500 m2/g for
ideal monolayered g-C3N4 [22].
Fang et al. [178] peeled bulk g-C3N4 (BCN) into 2D g-C3N4 NS
(CNNS) with the etching assistance of anhydrous ethylenediamine
(ADE) for the first time. As shown in Fig. 27a, the strong corrosivity of
AED can break down the hydrogen bonds existing between the CN layers
easily and pealed BCN into CNNS, and resulted in a changed color from
yellow to off-white (Fig. 27b). Caused by the relatively large specific
surface area of the CNNS (from 4.7 to 31.1 m2/g), a more stable
dispersion in liquid can be observed with an obvious Tyndall effect in
the solution after stored of 40 days (Fig. 27c). The formation of 2D NS
can be confirmed from TEM images (Fig. 27d to f) and a large lateral size
of more than 15 μm can be observed from AFM measurement (Fig. 27g).
Due to the size effect, the band gap of 2D CNNS was wider than that of
BCN, with energy band position of both CB and VB shifted toward more
positive direction (Fig. 27h). Even so, due to the dramatically enhanced
specific surface area of the special 2D structure, an excellent improved
H2 evolution ability was observed over the CNNS, which increased from
4.8 μmol/g/h to 35.3 μmol/g/h, about 7.4 times than that of BCN, as
well as good durability (Fig. 27i and j).
6.3.1.4. 3D nanostructure g-C3N4. 3D structure g-C3N4 keeps the
attractive merits of low dimension materials, such as high specific sur­
face area, sufficient active sites and good light absorption ability. At the
same time, 3D structure avoids the agglomeration of low-dimensional
structural units, and provides a three-dimensional interconnection
network for electron transport and ion diffusion, which benefit to the
improvement of photocatalytic performance [181–188]. Many strate­
gies including template and template-free method have been used for
the synthesis of 2D g-C3N4. A s shown in Fig. 28, Li et al. [184] reported
the fabrication of 3D g-C3N4 by using SiO2 as a hard template through a
thermal treatment strategy. Huang et al. [181] fabricated the 3D hollow-
sphere structure g-C3N4 through a template-free heat polymerization
route. In 2022, Wang et al. [188] synthesized 3D network structure g-
C3N4 through the assembly of g-C3N4 nanowires by using hydrothermal
and calcination processes. The morphology and special structure of the
obtained samples depends on the precursors and synthesis procedures.
Luo et al. [182] fabricated three-dimensional network structure g-
C3N4 via a chemical tailoring route (Fig. 29a). Firstly, bulk g-C3N4 was
tailored into little pieces with a small amount of heptazine ring
repeating units with -NHx and -OH groups by treating with hot
concentrated nitric acid. Meanwhile, the structural hydrogen bonding
between melon units in bulk g-C3N4 could be broken by the strong
oxidation of nitric acid, Thus, when pH was close to neutral, these pieces
could self-assemble into the nanorod-like precursor via hydrogen bonds
like N-H⋅⋅⋅O, N-H⋅⋅⋅N in layers and π-π conjugation between layers. After
then, these nanorods precursor intertwined to form a 3D network
structure (Fig. 29b and c). The as-fabricated 3D structure the g-C3N4
exhibited 6.7 times higher specific surface area than that of bulk g-C3N4
(Fig. 29d), at the same, the charge carrier transfer resistance decreased
from 1812 kΩ to 657.5 kΩ (Fig. 29e). The increased specific surface area

Fig. 27. (a) Diagrammatic sketch for the exfoliation of CNNS. (b) Photographs of BCN and CNNS, (c) status of 5 mg photocatalysts in 10 vol% TEOA aqueous solution
after natural sedimentation for different days. (d-f) TEM and HR-TEM images of CNNS. (g) AFM image showing the lateral dimensions and thickness of CNNS. (h)
bandgap structures of BCN and CNNS, (i) comparison the visible-light photocatalytic H2 evolution of BCN and CNNS, (j) wavelength dependent H2 evolution of
CNNS. The inset is photocatalytic durability test for CNNS under visible light irradiation. Adapted with permission from ref [178]. Copyright 2017 American
Chemical Society.

22
D. Ma et al.
Fig. 28. The fabrication of through controlling the assemble of 3D g-C3N4 by using different strategies (a) SiO2-based template method. Adapted with permission
from ref [184]. Copyright 2021 Elsevier. (b) heat polymerization method. Adapted with permission from ref [181]. Copyright 2019 Elsevier. (c) Self-assembly
method. Adapted with permission from ref [188]. Copyright 2019 Elsevier.
and the decreased charge transfer resistance resulted in a 5.9 times
improved H2 evolution ability (Fig. 29f).
Qian et al. [186] fabricated 3D porous g-C3N4 by using a NaCl-
assisted ball-milling strategy. As shown in Fig. 30a, melamine is first
surrounded by NaCl crystals after ball-milling. Then, the situ generated
g-C3N4 sheets are pierced and separated by NaCl crystals during the
annealing process owing to the higher melting point of NaCl. Finally, 3D
porous g-C3N4 is obtained after removing of NaCl through the water
treatment. It was found that the porosity and micro structure of the 3D g-
C3N4 can be controlled through the addition concentration of NaCl and
thus have direct effect on the photocatalytic behaviors of the porous
samples. As shown in Fig. 30b and c, compared to M0 (without the
addition of NaCl), M90 (the mass ratio of melamine and NaCl was 1:90)
undergoes an increased light absorption ability in UV region a lighter
color, considering that the band gap of M90 is larger than that of M0, the
increased UV light harvest ability indicates a better light adsorption
ability due to the formation of porous structure. With the merits of this
unique structure, the obtained 3D porous g-C3N4 exhibited a hydrogen
evolution rate of 598 μmol/h/g (Fig. 30d and e) with an apparent
quantum yield of 3.31 % at 420 nm for photocatalytic H2 generation,
which is much higher than that of the bulk g-C3N4. Similarly, the
fabrication of 3D open porous g-C3N4 was reported by Chen and co­
workers by using the salt assisted method [183].
Chen et al. [187] constructed a 3D porous structure photocatalyst
through the assembly of ultra-thin g-C3N4 NSs, which was successful in
the complete decomposition of water into hydrogen and oxygen under
visible light. The 3D interconnected framework consisted of highly
23
Coordination Chemistry Reviews 500 (2024) 215489
crystalline NSs provides a path for the quickly transfer of charge carriers,
at the same time, the formed 3D network prevents the agglomeration of
the NSs and endows the photocatalyst with good durability of more than
100 h (Fig. 31).
6.3.2. Construction of porous structure g-C3N4
The porous structure plays important role in the photocatalytic re­
action process. Generally speaking, porous structure can increase the
specific surface area and active sites of catalysts, and promote the
transport and diffusion of carriers and ions. In addition, porous structure
can obviously reduce the reflectance of light and increase the absorption
coefficient of light. Moreover, some special pore structure can be used as
a micro-reactor to provide uniform chemical micro-environment for the
photocatalytic reaction [189–197]. Based on the above-mentioned
merits, the construct of porous g-C3N4 (PCN) has attracted many re­
searches. Up to now, template methods are widely utilized in the
fabrication of porous structure g-C3N4. In a typical thermal condensation
polymerization, both hard template method and soft template method
are used [118,198–207]. As shown in Fig. 32 and Fig. 33, Zhang et al.
[197] synthesized PCN by using colloidal silica (SiO2) and dicyandia­
mide (DCDA) as the hard template and precursor, respectively. Wang
et al. [205] fabricated PCN by using CaCO3 as the hard template. Chen
and coworkers [206] reported the fabrication of PCN by using carbon
nanotube as a novel recyclable hard template. Li et al. [207] fabricated
the heterogeneous TiO2/g-C3N4 with a layered mosaic stack structure by
using montmorillonite as a hard template. All of these methods can
successfully obtain the g-C3N4 with designed porous structure. Khamrai
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 29. (a) Schematic illustration of the synthetic route for 3D g-C3N4 NR, (b) and (c) are separately the SEM and TEM images of 3D g-C3N4 NR, (d) Nitrogen
isothermal adsorption–desorption curves (Pore volume distribution inset), (e) electrochemical impedance spectra (the equivalent circuit impedance model inset) and
(f) H2 evolution ability of 3D g-C3N4 NR and bulk g-C3N4. Adapted with permission from ref [182]. Copyright 2019 Elsevier.

et al. [189] fabricated mesoporous g-C3N4 by using silica (SiO2) nano­
spheres as template and mono-cyanamide as precursor. The obtained
mesoporous catalyst has abundant ordered pore size of 5–10 nm, which
provides sufficient active sites for the photocatalytic reaction. Wang
et al. [118] reported the preparation of PCN by using NaH2PO4⋅2H2O as
a soft template. Chen e al. [208] fabricated the PCN by using sulfur-
bubble as a soft template. Yan [209] fabricated PCN by using Pluronic
P123 surfactant as soft template and melamine as precursor.
Hard template method is simple to control, but the corrosive reagents
usually are used to remove the templates, which faces the risk of bring
damage to environment, but the use of soft template method faces the
problems such as low polymerization and the residue of template, which
affect the photocatalytic activity [192,193,210]. Thus, the template free
method is an alternative novel and popular strategy in the fabrication of
PCN [190–196]. She et al. [192] fabricated oxygen-doped porous ultra-
thin g-C3N4 NSs (PUOCNs) by combing the calcined method and
chemical oxidation method at room temperature with a template-free
procedure. HNO3 and H2SO4 are utilized to destroy the 2D plane and
generate porous structure in the as fabricated g-C3N4 NSs (Fig. 34a). It
can be observed from the TEM images that the g-C3N4 are of the NS
structure with lots of non-uniform networks (Fig. 34b and c).
Cheng et al. [193] fabricated porous g-C3N4 with disordered
nitrogen-defect-rich character by using biuret as a new precursor
(Fig. 35a), and the formation of porous structure on the surfaces of NSs
can be confirmed by the TEM images in Fig. 35b and c. It was found that
the as-fabricated samples displayed much improved H2 evolution ability
than that of pristine g-C3N4 and high AQY of about 14.49 % at the
wavelength of 420 nm (Fig. 35d and e). The authors thought that the
ultra-thin and porous features synergistically promoted the effective
separation of photo-generated carriers by shorting the migration dis­
tance and provided abundant reactive sites for the photocatalytic reac­
tion (Fig. 35f). Wu et al. [190] synthesized Co and Mo co-doped
mesoporous g-C3N4 with high specific surface area by using a
template-free method. This bimetallic component and mesoporous
structure can provide more active sites, improve light absorption ca­
pacity, promote photogenerated carrier separation and enhance mass
transfer, thus significantly improving the photocatalytic ability of pure
g-C3N4.
As a typical surface reaction, PHE process significantly relies on the
light response ability and the exposure of active reaction sites of the

24
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 30. (a) Schematic illustration of the synthesis procedure of porous g-C3N4, (b) UV–vis diffuse reflectance spectra and (c) schematic illustration of the band
structure of M0 and M90 samples. (d) Amount of H2 evolution and (e) hydrogen evolution rate of the obtained samples under visible-light irradiation. Adapted with
permission from ref [186]. Copyright 2019 American Chemical Society.

Fig. 31. (a) Schematic illustration of the bottom-up supramolecular self-assembly route for synthesizing 3D g-C3N4 NS. (b) SEM image, (c) TEM image (HRTEM
image inset) and (d) AFM image of 3D g-C3N4 NS. (e) and (f) are separately the time-dependent overall water splitting activity and repeated cycles of overall water
splitting over 3D g-C3N4 NS. Adapted with permission from ref [187]. Copyright 2019 Elsevier.

photocatalyst. Morphology and structure manipulation plays important
role in improving the light absorption ability and facilitating the expo­
sure of active sites. Loose and porous 3D structure is in the most ex­
pected because it not only provides sufficient active sites for
photocatalytic reaction, but also benefits to the harvest of incident light
through the multiple reflections scattering of light in the porous
structure.
7. Exogenous modification of g-C3N4
7.1. Co-catalyst decoration
Despite many self-modification methods have been made in
improving the intrinsic properties of pure g-C3N4, the PHE activity of
single g-C3N4 is still limited by the serious charge carrier recombination,
insufficient surface catalytic sites, slow surface reaction rate and serious
adverse reaction. The introduction of co-catalysts plays crucial roles in
driving the mentioned problems. Co-catalyst itself is inert in photo­
catalytic reaction, but it has positive effects on suppressing charge
recombination, increasing reactive active sites and alleviating catalyst
photo corrosion after coupling with semiconductor catalysts. In some
cases, the co-catalyst can even activate the reactant molecules, thereby
reducing the activation energy and improving the surface REDOX re­
action kinetics, which effectively improves the photocatalytic reaction
efficiency [211–214].
Up to now, the commonly used co-catalysts includes metal-based co-
catalysts and metal-free co-catalyst. Metal nanoparticles are the most
commonly used co-catalysts in photocatalytic reactions. As shown in
Fig. 37a and b, the formation of Schottky barrier between metal co-
catalysts and g-C3N4 is the fundamental reason for the improvement

25
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 32. The fabrication of PCN by hard template method. (a) Schematic diagram of the preparation process for DMCN samples. Adapted with permission from ref
[197]. Copyright 2019 Royal Society of Chemistry. (b) Scheme for preparation of porous 2D graphite-phase polymeric carbon nitride (pGPPCN) using CaCO3 particles
as the template. Adapted with permission from ref [205]. Copyright 2015 Royal Society of Chemistry. (c) Schematic illustration of the synthesis of porous g-C3N4 via
using CNT as hard template. Adapted with permission from ref [206]. Copyright 2019 Wiley-VCH. (d) schematic diagram of the synthetic route of heterogeneous
TiO2/g-C3N4 with a layered mosaic stack structure. Adapted with permission from ref [207]. Copyright 2021 Elsevier. (e, f) TEM images of the porous g-C3N4.
Adapted with permission from ref [118,198]. Copyright 2021 Elsevier.

Fig. 33. The preparation of PCN by sing soft template method. (a)Schematic for the formation of porous sulfur-mediated g-C3N4. Adapted with permission from ref
[208]. Copyright 2015 Royal Society of Chemistry. (b) Schematic illustration for the formation of the hollow worm-like graphitic carbon nitride. Adapted with
permission from ref [118]. Copyright 2021 Elsevier.

of H2 generation efficiency [215–217]. Due to the difference of Fermi
level, a built-in electric field formed between metal co-catalyst and g-
C3N4, which provides strong drive force to facilitate the efficient sepa­
ration of electron-hole pairs and inhibits the backflow of photogenerated
electrons from co-catalyst to g-C3N4, thus improving the utilization ef­
ficiency of charge carriers. It is remarkable that, some noble metals, such
as Au [218–220] and Ag [221–223], have special Surface Plasmon
Resonance (SPR) effect, which further promotes the utilization of elec­
trons thorough the hot electron injection procedure (Fig. 36c). Many
noble metal and noble metal-based co-catalysts, such as PtS [224] and
RhxP [225], are utilized as co-catalysts in improving the HER of single g-
C3N4. However, from the point of sustainable development, the limited
storage and high cost of precious-metal-based cocatalysts restrict their
large-scale application.
In recent years, the inexpensive and earth abundant elements such as
NiP [226], FeCu [227], and some compounds including metal hydrox­
ides [228], metal phosphides [229], metal oxides [230,231], metal
borides [232], metal carbides [214], and metal sulfides [233–236] have
been studied as the alternative co-catalysts. Different from noble
metallic co-catalysts, these noble- metal-free co-catalysts trap the elec­
trons from g-C3N4 through the formation of band alignment with g-
C3N4. As displayed in Fig. 36d and e, the narrow band gap semi­
conducting co-catalysts harvest electrons from g-C3N4 thereby acceler­
ating the charge carrier separation. Yuan et al. [235] decorated ultra-
thin g-C3N4 NSs with MoS2 co-catalyst, which displayed more excel­
lent HER performance than the decoration of 3 wt.%Pt. Tong et al. [236]
modified g-C3N4 NSs with graphene oxide as co-catalyst and found that
the introduction of graphene oxide co-catalyst significantly improved
the photocatalytic performance of pure g-C3N4. Zhang et al. [234]
modified S doped g-C3N4 with CoS2 co-catalyst and obtained favorable
noble-metal-free photocatalytic activity for H2 evolution under visible-
light irradiation (11.55 μmol/h), which was around 578 times that of
pure g-C3N4 (Fig. 37a). Co-S bonding between CoS2 and S-doped g-C3N4
strengthen the directed transfer of photo-generated electrons from S-
doped g-C3N4 to CoS2 and contributes to the generation of hydrogen
(Fig. 37b and c).

26
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 34. (a) Schematic illustration of preparing PUOCNs. (b) and (c) are the typical TEM images with different magnifications of the PUOCNs. Adapted with
permission from ref [192]. Copyright 2015 Elsevier.

Except for the inert property of co-catalyst, the morphology and insufficient contact between co-catalyst and catalyst caused by the
structure of co-catalyst also effect strongly on the photocatalytic activity improper fabrication method is a headache trouble that limited the
of g-C3N4. Fu et al. [167] decorated g-C3N4 with hollow cobalt sulfide separation of charge carriers, defects engineering and in-situ growth
(CoSx) polyhedrons derived from ZIF-67 metal–organic frameworks as a method may provide efficient paths in forming intimate contact between
co-catalyst. The obtained CoSx/g-C3N4 composites showed 52 times co-catalyst and g-C3N4.
higher H2 evolution ability than that of pure g-C3N4 (Fig. 38a to e). Due
to the difference in Fermi level between g-C3N4 and CoSx, the photo­
7.2. Heterostructure catalysts
generated electrons in the CB of g-C3N4 will transfer to the surface of
CoSx, the CoSx with zero-approaching adsorption free energies of H2 acts
In a single g-C3N4 photocatalyst, the photogenerated electrons in the
as H2 generation active sites and reduces H+ to H2 (Fig. 38f). At the same
CB are easily return back to the VB and recombined with hole, which is
time, the excellent improved photocatalytic performance can be
quite harmful to the photocatalytic reaction. Constructing hetero­
ascribed to that ①the polyhedral morphology provides more surface
structures by coupling g-C3N4 with other energy band matched semi­
active sites for H2 generation, ② the hollow structure favors mass
conductors is an attractive strategy in the development of high active
diffusion and enhancing the utilization of solar energy, ③ the possible
photocatalysts [241–247]. The suitable energy band position and special
photothermal effect in the hollow black-colored CoSx raises the surface
flexible structure make g-C3N4 a superior mate for the construction of
temperature and beneficial for the mass diffusion/transfer and H2
semiconductor heterojunctions with matched band structure and
adsorption (Fig. 38g).
controllable interface contact. The fundamental reason for the remark­
For co-catalyst, small size and high distribution are expected to
able improved photocatalytic performance of heterojunction is the
obtain high active sites and thus to accelerate the surface reaction. With
complementary advantage between different semiconductors, which
the development of modern synthesis technology, the size of metal
usually lead to the extended light absorption, increased active site,
nanoparticles is gradually reduced even to the single atom scale
accelerated charge carrier separation, and improved photo stability
[237–241]. Due to the unique unsaturated coordination environment,
[15,195,248–250]. When combined with other semiconductors, the in­
the loading of single atomic co-catalyst can improve the intrinsic activity
ternal electric field formed at the interface can effectively promote the
of catalytic sites [238], maximum the utilization rate of metal atoms and
exciton dissociation in g-C3N4, accelerate the separation of photo­
greatly increase the reactive active sites. At the same time, the N-rich
generated charge carriers, and thus improve the efficiency of the pho­
nature and the good coordination ability between N atoms and metal
tocatalytic system. In addition, the introduction of g-C3N4 may also
atoms make g-C3N4 an ideal carrier for the preparation of single atomic
inhibit the photo corrosion of other semiconductors, such as CdS, and
co-catalysts with high loading capacity and high stability, which pro­
improve the stability of photocatalytic systems. Obviously, the forma­
vides new opportunity for the development of high activity photo­
tion of heterostructure dramatically broadens the types of semi­
catalytic system. For example, Chen et al. [239] loaded single atomic Pt
conductor catalysts available for photocatalysis, and significantly
co-catalyst on the surface of g-C3N4, Jiang et al. [240] fabricated Ag
expands the space for improving the photocatalytic performance of
monoatomic co-catalyst by using g-C3N4 as the support through the C-N
semiconductors compared with the self-modification strategies.
co-coordination, which achieved efficient photocatalytic hydrogen
Energy band structure design and the interface structure control are
production by reducing the excitation charge transport energy barrier.
two crucial factors that affect serious on the performance of hetero­
Different from the self-modification strategy, the loading of co-
structure photocatalysts: the band matching relationship between two
catalysts provides extra active sites on the surface of g-C3N4, the for­
semiconductors determines the charge carrier transfer mechanism and
mation of interface electronic field between g-C3N4 and co-catalysts
REDOX capacity of a heterostructure, the directional transfer and rapid
accelerates the migration of photogenerated electrons from the surface
separation of charge carriers, as well as the thermodynamic re­
of g-C3N4 to the co-catalyst and thus benefiting to the separation of
quirements of the target reaction can be met through constructing het­
charge carriers. The enhancement effect of co-catalyst on the PHE per­
erojunctions with matched energy bands. At the same time, the interface
formance of g-C3N4 is influenced by many factors, such as the size,
quality of heterojunction has important influence on the transfer ability
dispersity and deposition amount of co-catalyst, optimizing the structure
and separation efficiency of charge carriers, it is an efficient strategy to
of co-catalyst and controlling the deposition amount of co-catalyst have
facilitate the charge carrier migration and improve the photocatalytic
positive significance in obtaining higher PHE active. In addition, the
efficiency through improving the interface contact quality between

27
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 35. (a) Synthetic route illustration for CN-UNS, (b) and (c) TEM images for CN-UNS, (d) Photocatalytic H2-evolution activities and (e) AQYs at different
wavelengths and UV–vis spectrum for CN-UNS, (f) schematic illustration of enhanced photocatalytic performance by the synergistic effect of the ultrathin and porous
features and N vacancy. Adapted with permission from ref [193]. Copyright 2021 Elsevier.

semiconductors [251–256].
7.2.1. Energy band matching principle
Due to the moderate energy band position, g-C3N4 can form an en­
ergy band matched heterojunction system with most materials, a type I,
type II, Z-scheme or S-scheme charge transfer pathway will form on the
interface of the semiconductors, which provides main drive force for the
effective separation of carriers in space. At the same time, the band
position of the semiconductor should match the REDOX potential of the
target product, so that to provides enough REDOX capacity to drive the
photocatalytic reaction.
To endows a heterostructure with the most beneficial charge transfer
process, in addition to the selection of semiconductors with suitable
band locations, rationally control and adjust the band structure of g-
C3N4 and select the electron transfer mediators are commonly used.
Taking the couple of g-C3N4 and indium zinc (ZnIn2S4) as example, g-
C3N4 and ZnIn2S4 formed a type I energy band alignment, in order to
improve the photocatalytic ability, Wang et al. [257] introduced defects
into g-C3N4 to change the band energy position of g-C3N4. As a result, a
Z-scheme energy transfer pathway formed between the two semi­
conductors, thus efficiently facilitating the charge carrier separation and
achieving high photocatalytic performance with the AQY of 18.2 % at
the wavelength of 420 nm. In addition, suitable electron transfer me­
dium is also crucial in facilitating the interfacial charge transfer between
semiconductors. Li et al. [258] deposited metal on the interface of g-
C3N4/WO3 heterostructure and studied the effect of metal’s Fermi level
position on the interfacial charge transfer behaviors. They found that the
Fermi level of Ag is too high while the and the Fermi level of Au is too
low, neither Ag nor Au fail to drive the photogenerated electrons to
transfer between the two semiconductors. By contrast, the Fermi level of
Cu located between the Fermi level of WO3 and g-C3N4, thus can transfer
the photogenerated electrons in the CB of WO3 to the VB of g-C3N4 and
forming an efficient indirect Z-type carrier transport mechanism.
In recent years, with the development of theoretical research,
calculation based on the first principles of density functional theory
provides a theoretical model and ground for the design of

28
D. Ma et al.
Fig. 36. (a) Energy band diagrams of metallic co-catalyst and g-C3N4 before contact, (b) after Schottky contact, (c) coexistence of Schottky barrier and SPR effect
between g-C3N4 and noble metal co-catalyst, (d) energy band diagrams of semiconductor co-catalyst and g-C3N4 before contact, (e) after contact.
heterostructure photocatalysts with matched band structure. Based on
theoretical calculation, Wang et al. [259] proved that combination of g-
C3N4 and Ag3VO4 can reduce the mixed electron density of C atom and
nearby N atom in g-C3N4, thus to induce the transfer of electrons to the
Ag atom and then to the CB of Ag3VO4, at the same time, the photo­
generated holes transferred from Ag3VO4 to the VB of the g-C3N4 and
form a type II charge transfer pathway and greatly promote the inter­
facial charge transfer and improve the photocatalytic activity. With the
high-speed development of the theoretical calculation, the understand­
ing to the band structure relationship of composites is improving, which
will further promote the design of energy band matched heterojunction
system and the rapid development of controllable preparation methods.
7.2.2. Surface optimality principle
For heterostructure photocatalyst, semiconductor surface is the
dominant site for the photocatalytic while the separation and transfer of
photogenerated charge carriers mainly occur at the interface of heter­
ostructure. Hence, the microstructure of semiconductor surface and
interface will directly affect the transfer and reaction efficiency of
charge carriers, and eventually significantly affect the photocatalytic
performance. Considering the key roles of the surface/interface struc­
ture of heterostructures in the photocatalytic reaction process, the
design of heterostructure photocatalyst should base on the optimization
of the surface/interface structure to maximize the utilization efficiency
of charge carriers.
In order to optimize the surface structure of heterogeneous catalyst,
the thickness and morphology of the semiconductors should be
controlled to meet the requirements of light transmission depth and
avoid the shielding effect when forming heterogeneous structures. At the
same time, researchers should give priority consider to the exposure of
the highly reaction active surface to ensure the sufficient contact be­
tween the active sites and the reaction substrate, thus to improve the
probability of surface photocatalytic reaction. In addition, the surface
crystal structure should be benefit to the adsorption and activation of
29
Coordination Chemistry Reviews 500 (2024) 215489
reactive molecules [162,254,255,260–264]. For g-C3N4, the construc­
tion of 2D NS structure is conducive to the sufficient exposure of the
atoms with unsaturated coordination on the surface and is benefit to the
exposure of effective reactive active sites. At the same time, the 2D
planar of g-C3N4 provides in situ nucleation and growth sites for the
second semiconductor and thus is benefit to the formation of intimate
contacted heterostructure catalyst. In addition, it is also feasible to the
introduce microporous structures on the surface of g-C3N4 by secondary
treatment, which can create new active edges and increase the reactive
active sites and thus to further improve the photocatalytic performance.
7.2.3. Interface optimality principle
7.2.3.1. The formation of intimate contacted interface. As was
mentioned, the interface between semiconductor is the main place for
the separation and transfer of charge carriers, thus, it is necessary to
strengthen the bonding between different materials as much as possible
to reduce the interfacial resistance of carrier transport. The contact
tightness can be improved by regulating the formation mode of the
contact interface, for example, the in situ epitaxial growth method can
be used to form a tight chemical bond between g-C3N4 and other pho­
tocatalysts for efficient carrier transport. Another commonly adopt
strategy is to form heterogeneous structures based on the Van der Waals
forces between g-C3N4 and other semiconductors. This kind of combi­
nation can get rid of the restriction of lattice matching requirements,
achieve tight electronic coupling at the interface, reduce the charge
transfer barrier, and thus greatly improve the transfer rate of charge
carriers. For example, Zhu et al. [260] constructed the phosphoene/g-
C3N4 Van der Waals heterojunction through a ball milling method, the
tight and stable contact interface formed between the two semi­
conductors facilitates the efficient charge separation and transfer. In
addition, high quality heterojunction interfaces can be constructed by
selecting two semiconductor materials with similar interface properties.
For example, g-C3N4 is easy to form intimate contact with organic
D. Ma et al.
Fig. 37. (a) UV–vis spectra for CN, CN-HTS, CN-3CoS2 and CoS2, (b) visible-driven photocatalytic H2-evolved rates for the samples, (c) Illustration of the mechanism
about enhanced photocatalytic ability for CoS2/S-doped g-C3N4. Adapted with permission from ref [234]. Copyright 2020 Elsevier.
semiconductors or carbon-based materials with similar π-π conjugate
structure through intermolecular interaction. Chen et al. [252]
confirmed that the π-π interaction formed between amorphous poly­
fluorene materials (PFs) and g-C3N4 contributes to the effective transfer
of photogenerated charge carriers. Specially, the construction of ho­
mogeneous junction between two different structures of g-C3N4 was also
reported to be efficient in obtained excellent photocatalytic activity due
to the intimate contacted interface and the rapid charge transfer in the
homojunction interface.
7.2.3.2. Improve the interface contact area. Another principle in opti­
mizing heterojunction interface is to maximize the interface contact as
much as possible, thus to provide a rich transmission channel for the fast
interfacial transfer of charge carriers. The lowest efficiency hetero­
structure is the “hybrid” formed by the simple mixing of different
semiconductors, the point contacted interface in the simple mixed
hybrid usually resulting in limited effective interface contact area and
low efficiency of interfacial charge separation. In contrast, “core–shell”
heterostructure has a larger effective contact area, but it is crucial to
take the effective excitation of “core” semiconductor into consideration
because one semiconductor is completely coated by another one. At the
same time, the sufficient exposure of high active surface in the “core–­
shell” structure is also important in achieving high utilization efficiency
of the charge carriers [261–264]. The hollow “core–shell” hetero­
structure provides a solution to the problems existing in the coated
heterojunction: the intimate contacted interface between hollow core
and the shell layer guaranteed a high charge carrier separation
30
Coordination Chemistry Reviews 500 (2024) 215489
efficiency, at the same time, the hollow structure not only conducive to
mass diffusion and transfer, but also can cause multiple light reflection
in the cavity to improve the utilization efficiency of solar spectrum
[247,265–268]. In addition, as a hot research direction in recent years,
2D to 2D (2D/2D) heterostructures can make full use of the structural
advantages of g-C3N4 to maximize the interface contact area [269–272].
Meanwhile, planar structures greatly shorten the distance of photo­
generated charge carriers migrating from the inside of the material to
the space charge region near the interface or the surface reaction sites.
Jiang et al. [273] reported that 2D-2D hexagonal boron nitride (H-BN)/
g-C3N4 heterojunction photocatalyst. The ultrathin heterostructure not
only improved the charge transfer efficiency, but also exposed more
active sites, thus greatly improving the photocatalytic performance.
7.3. Category of g-C3N4-based heterostructure
Generally, the relative energy band structure and electron transfer
pathway is the most considered factor in the construction of hetero­
structure. The current studied g-C3N4-based heterostructures can be
classified into g-C3N4/semiconductor heterojunctions, g-C3N4/metal
heterojunctions, g-C3N4/carbon heterojunctions, g-C3N4/MOF hetero­
junctions, and the special g-C3N4/g-C3N4 homojunctions according to
the property of the second materials. As the C3N4/metal heterojunctions
have been discussed in the chapter of metal co-catalyst modified g-C3N4,
we will emphatically introduce the other mentioned heterojunction
catalysts in this chapter.
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 38. (a) Schematic illustration for the fabrication of CoSx/g-C3N4 composites. (b)TEM images of hollow CoSx polyhedrons. (b) (c) and (d) are separately the TEM
images of hollow CoSx, g-C3N4 NSs and the 2 % CoSx/g-C3N4 composite, (e) Photocatalytic H2 generation rate of g-C3N4 and CoSx/g-C3N4 composites with different
CoSx contents (1–10 %) under visible light (λ ≥ 400 nm) irradiation, (f) Possible mechanism for photocatalytic H2 evolution over CoSx/g-C3N4 composite photo­
catalyst. (g) Schemes of light path and photothermal effect in the hollow CoSx polyhedron. Adapted with permission from ref [167]. Copyright 2018 American
Chemical Society.

7.3.1. g-C3N4/semiconductor heterostructures
When two semiconductors with different band structures are closely
contacted, an internal electric field formed at the interface between
semiconductors will drive the directional movement of photogenerated
electrons and holes. Matched energy band structure is the key
consideration in choosing the second semiconductor for constructing g-
C3N4-based heterojunction. Commonly, type I, type II, Z-scheme and S-
scheme heterojunctions can be formed according to the transfer mech­
anism of photogenerated carriers between semiconductors.

Fig. 39. Schematic diagram of charge transfer for (a) type I (b) and (c) type II, (d) direct Z-scheme, (e) indirect Z-scheme, (f) S-scheme heterojunction systems. (“PS”
is the abbreviation of “photocatalysts”.

31
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

7.3.1.1. Type I and type II heterostructure. As shown in Fig. 39a, type I
heterojunction featured with a nested band structure between semi­
conductors, the valence band and conduction band of the narrow
bandgap material are located in the gap band of the wide bandgap
material. Under light, photogenerated electrons and holes respectively
transferred from the wide band semiconductor to the narrow band
semiconductor. Due to the different transfer rates of photogenerated
electrons and holes, the recombination of photogenerated charge car­
riers can be efficiently suppressed. Type II heterojunction is the most
widely used in the construction of hetero photocatalysts, in which the
two semiconductors displayed interlaced energy band positions (as
shown in Fig. 39b and c), photogenerated electrons and holes separately
transferred along different direction and finally aggregated on different
semiconductors to drive the reduction and oxidation reactions, respec­
tively. In the practical experiment, most studied type II heterojunction
follow the diagram shown in Fig. 39b because the g-C3N4 occupied a
relative negative band position. Table 3 listed some reported g-C3N4-
based type I and type II heterojunction systems.
Due to the facile fabrication procedure and matched energy band
structure, the heterostructures constructed by TiO2 and g-C3N4 are the
most widely studied catalyst. Our group has carried out a lot of re­
searches on the construction of g-C3N4-based heterojunction catalysts.
For example, we reported the fabrication of C-TiO2@g-C3N4 core@shell
heterostructure by using an in-situ strategy [275], the adoption of in-situ
fabrication method contributes to the formation of highly intimate
contact interface. Due to the expanded light absorption caused by C
doping and the accelerated charge transfer between TiO2 and g-C3N4
semiconductors, the obtained hybrid displayed 23 times and 10 times
higher H2 evolution ability than that of TiO2 and g-C3N4 separately.
Narrow band gap semiconductor CdS (2.4 eV) has excellent light
absorption ability, but the serious photo-corrosion results in quickly
declined photocatalytic performance, Li et al. [276] fabricated CdS/g-
C3N4 hybrids by using an in-situ hydrothermal method, it was found that
the combination of CdS and g-C3N4 efficiently broaden the light ab­
sorption of g-C3N4 and about 10 wt% location of CdS lead to the H2
evolution rate 21 times greater than single g-C3N4 and 4 times greater
than that of pure CdS. Liu [277] revealed the structure and electron
transfer mechanism in the CdS/g-C3N4 by using the DFT study. Based on
the Bader charge analysis for the charge densities of the sample, it can be
found from Fig. 40a that the electrons transferred from g-C3N4 to CdS
across the interface, whereas the holes remained in the g-C3N4. The
accumulation of net charge resulted in the formation of a built-in in­
ternal electric field at the interface, which was benefit to the separation
of charge carriers. At the same time, it was observed from Fig. 39b that
the Fermi energy of g-C3N4 (− 4.34 eV vs AVS) was higher than that of
CdS (− 5.04 eV vs AVS), When the two semiconductors combined
together, the photogenerated electrons in g-C3N4 would transfer towards
CdS and form a g-C3N4-CdS direction internal electric field. Under the

Table 3
Comparison of H2 evolution ability over the g-C3N4-based type II, Z-scheme and S-scheme heterostructures reported in past few years.
Catalyst catalyst mass of Reaction solution Co- Light source R (H2) R (H2) of pure g-C3N4 Ref. (year)
type catalyst catalyst (μmol/g/ (μmol/g/h)
(mg) h)

Type II TiO2/holey g-C3N4 10 80 mL H2O and 20 mL 1 wt% Pt 300 W Xe lamp, >420 35.4 2.5 [378]
methanol nm (2021)
3 3
ZnIn2S4/g-C3N4 50 80 mL H2O and 20 mL 3 wt% Pt 300 W Xe lamp, >420 160.7 x10 26.6 x10 [379]
TEOA nm (2021)
g-C3N4 /CoAl LDH 50 90 mL H2O and 10 mL N/A 300 W Xe lamp, >420 34 trace [380]
TEOA nm (2020)
K7HNb6O19/g- 50 40 mL H2O and 10 mL without 300 W Xe lamp 359.89 9.05 [381]
C3N4 methanol (2022)
CeO2/g-C3N4 5 40 mL H2O and 10 mL N/A 300 W Xe lamp,>400 nm 229.75 N/A [382]
TEOA (2022)
g-C3N4 /ZnIn2S4 25 40 mL H2O and 10 mL 1 wt% Pt 300 W Xe lamp, >420 20,738 8447 [383]
TEOA nm (2022)
TiO2/g-C3N4 75 67.5 mL H2O and 7.5 mL 3 wt% Pt 250 W visible light 1041.6 182.2 [384]
TEOA (2020)
Z-scheme CoSeO3/g-C3N4 20 90 mL H2O and 10 mL N/A 300 W Xe lamp 1459.2 22.3 [385]
TEOA (2022)
CoS/g-C3N4 100 85 mL H2O and 15 mL 5 wt% NiS 300 W Xe lamp 1.93 trace [386]
TEOA (2022)
g-C3N4 /rGO/ 20 45 mL H2O and 5 mL N/A 300 W xenon arc lamp, 869.8 8.1 [387]
FeOOH TEOA 400–800 nm (2021)
B doped g-C3N4 50 90 mL H2O and 10 mL 1 wt% Pt 300 W Xe lamp, >300 32.94 N/A [122]
/g-C3N4 TEOA nm (2021)
g LaNiO3/g-C3N4 10 80 mL H2O and 20 mL N/A 300 W Xe lamp, >420 312.763 7.129 [170]
methanol nm (2021)
g-C3N4 /WO3 50 40 mL H2O and 10 mL 1 wt% Pt 300 W Xe lamp, >420 862 326 [221]
TEOA nm (2019)
g-C3N4 /ZnO/Au 30 80 mL H2O and 20 mL without 300 W Xe lamp, >420 158.5832 6.11886 [279]
methanol nm (2023)
3
TiO2/rGO/g-C3N4 5 16 mL H2O and 4 mL N/A 300 W Xe lamp 32 x10 0.345 x103 [285]
glycerol (2020)
g-C3N4 /Cu/MoS2 20 80 mL H2O and 20 mL N/A 300 W Xe lamp, >420 971.5 44 [287]
TEOA nm (2022)
S-scheme CdS/g-C3N4 5 0.25 M Na2S-Na2SO3 N/A 300 W Xe lamp, >420 15.3 0.005 [302]
nm (2020)
g-C3N4 /g-C3N4 10 90 mL H2O and 10 mL 3 wt% Pt 300 W Xe lamp, >420 5548.1 111.5 [343]
TEOA nm (2022)
WO3/g-C3N4 N/A 20 % of lactic acid 2 wt% Pt Full spectrum 982 583 [299]
(2019)
N-MoS3/S-g-C3N4 50 90 mL H2O and 10 mL N/A 300 W Xe lamp 658.5 28.8 [296]
TEOA (2021)
Bi2S3/g-C3N4 10 0.35 M of Na2S and 0.25 N/A 300 W Xe lamp 3394.1 1298.4 [243]
M of Na2SO3 (2021)

32
D. Ma et al.
Fig. 40. (a) Planar-averaged electron density difference for g-C3N4/CdS, the
cyan and yellow areas indicate electron depletion and accumulation, respec­
tively, (b) diagram of the band edge positions before and after contact of g-C3N4
and CdS. Adapted with permission from ref [275]. Copyright 2015 American
Chemical Society.
irradiation of simulated sunlight, the photogenerated electrons would
transfer from the CB of CdS to g-C3N4 under the drive force of internal
electric field and thus forming the type II energy transfer process.
Some multi-component metal compounds, such as bismuth tungstate
(BiWO6) [276], bismuth chloride oxide (BiOCl) [277,278], indium zinc
sulfide (ZnIn2S4) [279,280], strontium titanate (SrTiO3) [281,282] and
so on, have unique advantages such as variable composition and rich
spatial structure, which provides the possibility of flexible regulation of
heterojunction band configuration and surface interface. Yin et al. [278]
fabricated g-C3N4/BiOCl heterojunction by dispersing g-C3N4 on the
surface of BiOCl microspheres, the formed p-n junction was responsible
for the improved separation efficiency of photogenerated electron-hole
pairs, and thus the higher photocatalytic activity.
7.3.1.2. Z-scheme heterostructure. For photocatalytic reaction, the pho­
togenerated electrons are expected to located in more negative CB po­
sition while the holes are expected to located in more positive VB
position, thus to obtain higher photocatalytic performance. Although
type I and type II heterojunctions can suppress the recombination of
33
Coordination Chemistry Reviews 500 (2024) 215489
photogenerated carriers, this effect is at the cost of reducing the REDOX
capacity of carriers. It’s a challenge to achieve the efficient separation
while maintaining the high REDOX abilities of charge carriers. As a
positive result of human learning about the natural process of photo­
synthesis, scientists have proposed a Z-scheme heterojunction system
recently, in which charge carriers can be efficiently separated without
the decline of REDOX abilities. As shown in Fig. 39d and f, the Z-scheme
system consisted of two semiconductors with interlocked band struc­
ture, the photogenerated electrons on the lower CB of photocatalyst I (PS
I) can transfer and recombined with the holes on the high VB of pho­
tocatalyst II (PS II), while the electrons with more reduction ability in
the CB of PS II and the holes with more oxidizing ability in the VB of PS I
are retained and participate in the photocatalytic reaction. Tan et al.
[283] constructed Z-scheme heterojunction by combining 2D ZnIn2S4
with g-C3N4 through an in-situ growth strategy, by the means of
morphology control, interfacial regulation, and energy band matching,
the obtained 2D/2D ZnIn2S4/g-C3N4 heterostructure displayed an
enviable photocatalytic hydrogen production rate of 14.799 mmol/g/h,
which is obviously better than that of bare ZIS and CN.
Due to the similar energy band alignment, there is often coexistence
and competition between type-II and Z-scheme charge-transfer path­
ways in a semiconductor–semiconductor heterojunction. Therefore,
some noble metals such as Au [284,285] and Ag [286,287], non-noble
metals such as Cu [288], and other materials such as metallic MoS2
[289,290], carbon dots [291], as well as graphene oxide [292], has been
utilized as electron transfer media to promoting the transfer of charge
carriers between semiconductors to guarantee the formation of Z-
scheme (Fig. 39e). Focus on the formation of Z-scheme charge transfer
mechanism between semiconductors, our group introduced Au nano­
particles into the interface of g-C3N4 and C doped TiO2 [289]. As shown
in Fig. 41, compared with the C-TiO2@g-C3N4 core–shell structure
hybrid, the introduced Au nanoparticles resulted in a dramatically
improved PHE active, which was more than 40 times higher than that of
g-C3N4. The reactive intermediate species trapping and superoxide
radical quantification experiments revealed that the introduced Au
nanoparticles played crucial role in improving the photocatalytic per­
formance of the system, which worked as electron transfer bridge to
induce the change of charge transfer pathway from type II to the Z-
scheme procedure, thus facilitating the separation of charge carriers and
significantly improving the REDOX ability of electrons and holes
(Fig. 41d and e).
Zhu et al. [293] constructed g-C3N4/Cu/MoS2 Z-scheme hetero­
junction by a two-step calcination method (Fig. 42a), in which Cu
nanoparticles are embedded between g-C3N4 and MoS2. Through the
detection of reactive intermediate, it was revealed that the Cu nano­
particles acted as electron media to construct the electron transfer be­
tween two semiconductors and form a Z-scheme charge transfer
pathway. Feng et al. [294] constructed the Z-scheme CdS/g-C3N4 het­
erostructure by introducing carbon quantum dots between the two
semiconductors as electron transfer media (Fig. 42b). Chen and co­
workers [292] constructed g-C3N4/CQDs/InVO4 Z-scheme hetero­
junction by using carbon quantum dots as electron mediator (Fig. 42c).
It was found that the carbon quantum dots located between g-C3N4/
CQDs/InVO4 not only behave as mediator between InVO4 and g-C3N4 to
promote the efficient separation of charge carriers via the Z-scheme
pathway, but also greatly improve the light response ability of the
photocatalyst, thus significantly enhanced photocatalytic activity of the
catalyst. Z-scheme heterojunction greatly promote the separation of
photogenerated electron-hole and maintain the REDOX ability of pho­
togenerated carriers, thus has become an important direction in the
development of hetero photocatalysts in recent years.
Apart from noble metals, some non-noble metallic materials are also
used as charge bridge to construct Z-scheme heterojunction. Wu et al.
[295] introduced non-precious metal bismuth (Bi) between Bi2MoO6
and g-C3N4 as a bridge for charge transport and constructed a Z-scheme
heterojunction, which extremely expanded the absorption ability of the
D. Ma et al.
Fig. 41. (a) Schematic illustration of the preparation of C-TiO2@g-C3N4, (b) TEM image of the sample, (c) The average H2 production rates of C-TiO2, g-C3N4, TCN,
ACN, and TACN-x, (d) and (e) are the charge transfer mechanism in C-TiO2@g-C3N4 and C-TiO2@Au@g-C3N4 systems. Adapted with permission from ref [274],
copyright 2017 Elsevier and ref [289], copyright 2017 Wiley-VCH.
catalyst and resulted in rapid separation of photogenerated carriers. In
addition, carbon-based materials such as graphene have good electrical
conductivity and can form a larger contact area with semiconductor
components than metal particles, which is conducive to rapid charge
transfer and is also commonly used as charge transport medium in g-
C3N4 heterojunctions. For example, Jo et al. [295] constructed a Z-
scheme CdS/g-C3N4 heterojunction using Reduced Graphene Oxide
(rGO) as the conductive mediator. Compared with the samples without
rGO, this catalyst had a significantly increased photocurrent response. It
is proved that rGO can effectively promote the separation and trans­
mission of photogenerated carriers as a charge transport medium, so as
to improve the utilization efficiency of carriers. Moreover, Fe3O4 with
variable valence of Fe2+/Fe3+ has also been proved to be available in
promoting the charge carriers between CdS and g-C3N4 to construct Z-
scheme heterojunction [297].
7.3.1.3 S-scheme heterostructure. Recently, some researchers point out
that although Z-scheme heterojunction benefit to the charge separation,
the accurate charge transfer mechanism is still controversial [298–300].
The proposal of step scheme (S-scheme) charge transfer mechanism
have been a new research hotpot, in which the difference in the Femi
level between semiconductors provide dominant drive force for the
transfer of charge carriers [301–305]. When two different semi­
conductor combined, electrons on the semiconductor with a smaller
34
Coordination Chemistry Reviews 500 (2024) 215489
work function spontaneously migrate to the semiconductor with higher
work function until the equilibrium of Fermi level and thus form a local
built-in electric field. Driven by the built-in electric field, the electrons in
the CB with lower reduction ability and holes in the VB of lower
oxidation ability recombine under the action of Coulomb force while the
electrons and holes with higher REDOX ability are maintained
[12,306,307].
Many heterojunctions have successful constructed S-scheme system,
Zhang et al. [304] constructed S-scheme heterojunction between BiOBr
and g-C3N4, Jiang et al. [306] reported the formation of S-scheme en­
ergy transfer pathway between sulfur-doped g-C3N4 and g-C3N4. Li et al.
[307] reported the formation of S-scheme charge transfer procedure
between Bi2MoO6 and g-C3N4. The formed S-scheme heterojunction
have been proven to be efficient in obtaining high H2 evolution per­
formance. Ren and coworkers [308] fabricated S-scheme heterojunction
through in situ hydrothermal growth of 2D CdS NSs on g-C3N4. Fu and
coworkers [305] combined WO3 ultra-thin NSs with 2D g-C3N4 NSs and
constructed a WO3/g-C3N4 heterostructure. The H2 evolution rate
increased from 583 μmol/g/h of pure g-C3N4 NSs to 982 μmol/g/h when
15 % of WO3 was loaded (Fig. 43a). Considering WO3 itself is inert in
photocatalytic reaction, the excellent improved H2 evolution ability can
be ascribed to the formation of heterojunction between WO3 and g-C3N4.
The detection of active intermediate was carried out to reveal the charge
transfer pathway in the hetero interface. As shown in Fig. 43b, according
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 42. (a) Synthetic illustration of CN-Cu-MS composites. Adapted with permission from ref [293]. Copyright by 2022 Wiley-VCH. (b) energy band diagram of the
Z-scheme electron transfer (CdS/CQDs/g-C3N4) mechanism. Adapted with permission from ref [294]. Copyright by 2019 Elsevier. (c) efficiency of RhB degradation
in the presence of various scavengers (left) and possible photocatalytic mechanisms of Z-scheme heterojunction CV20/CQDs2 under visible-light irradiation (right).
Adapted with permission from ref [292]. Copyright by 2021 Wiley-VCH.

to the energy band position, the ⋅O–2 can only generated by the electrons
on the CB of g-C3N4 while the ⋅OH can only formed through the oxida­
tion reaction by the holes on the VB of WO3. electron paramagnetic
resonance (EPR) measurements were utilized to detect ⋅O–2 and ⋅OH
generated in the system and the results were shown in Fig. 43c and d. As
was observed, the DMPO-⋅OH signal was obviously over WO3 NSs and
15 %WO3/g-C3N4, while no DMPO-⋅OH signal is observed for pure g-
C3N4, suggesting that the photogenerated holes still stay in the VB of
WO3. Similarly, the strong DMPO-⋅O–2 signal detected over g-C3N4 and
15 % WO3/g-C3N4 composite indicates that the photogenerated elec­
trons are present in the CB of g-C3N4.Therefore, the charge transfer
pathway on the hetero-interface can be explained by using a S-scheme
mechanism. As shown in Fig. 43e, when g-C3N4 and WO3 are close to
each other, an internal electric field is formed at the interface due to the
difference in work function, the electrons transfer from g-C3N4 to WO3 to
equilibrate the work function and result in an upward bends of the
energy, while the band edge of WO3 bends downward due to the accu­
mulation of electrons. Under light irradiation, under the multi-drive
force of internal electric field, band edge bending and Coulomb inter­
action, some electrons from the CB of WO3 recombined with the holes on
the VB of g-C3N4, at the same time, the corresponding electrons on the
CB of g-C3N4 and the holes on the VB of WO3 were retained, thus formed
a S-scheme charge transfer procedure and extremely accelerated the
generation of H2.
Chen et al. [302] constructed S-scheme heterojunction of S-doped g-
C3N4 (SCN) and N-doped MoS2 (NMS) by a one-step thermal poly­
condensation method, the formation of imitate contacted hetero­
structure can be confirmed from the TEM and HRTEM images in
Fig. 44a. The as-prepared NMS/SCN with an NMS ratio of 19.3 wt%
showed the highest H2 generation rate of 658.5 μmol/g/h, which was
about 23 and 38 times higher than that of pure SCN (28.8 μmol/g/h) and
NMS (17.4 μmol/g/h), respectively (Fig. 44b). In Surface photovoltage

35
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 43. (a) Comparison of H2-generation activities of as-prepared samples under xenon lamp irradiation, (b) band structures of g-C3N4 and WO3 NSs. (c) and (d) are
separately the EPR spectra of DMPO-•OH in aqueous and DMPO-•O−2 in methanol dispersion in the presence of g-C3N4, WO3 NSs and 15 %WO3/g-C3N4, (e) the work
functions and the S-scheme charge transfer mechanism between WO3 and g-C3N4 under light irradiation. Adapted with permission from ref [305]. Copyright by
2018 Elsevier.

spectrum (SPV) spectra, 19.3 %-NMS/SCN had a stronger photo-
response signal than that of pure SCN and NMS (Fig. 44c), meaning
that the 19.3 %-NMS/SCN is more likely to promote efficient separation
of light-induced charge carriers. Fig. 44d and e are the calculated Fermi
energy of the samples, assuming that the type-II heterojunction was
formed, the photo-generated electrons and holes were transferred to the
CB and VB of NMS and SCN, respectively, and H2 would be produced on
the CB of NMS. However, the CB edge of NMS was too low (− 0.07 eV) to
provide enough driving force for a H2 evolution reaction. Hence, a S-
scheme charge transfer pathway would form between NMS and SCN.
Based on the formation of heterojunction between two different
semiconductors, the ternary and multi-component photocatalysts have
also made great progress in recent years. Compared with the binary
heterojunction, the multi-component heterostructures are more
complicated in the component, interface structure and the carrier
transport mechanism, and thus the PHE of the multi-component pho­
tocatalysts can be further improved by comprehensive integrating and
optimizing the properties of different materials. It is to say, the syner­
gistic effect among different components would be benefit to the light
absorption and the efficient charge separation and fast charge transfer,
thus provides broader space for the construction of high performance
photocatalysts. Gogoi et al. [309] reported a ternary heterojunction
catalyst consisted by Cd0.5Zn0.5S, g-C3N4 and MoS2, the as fabricated
ternary heterostructure has abundant hetero interfaces for the transfer
of charge carriers, which greatly inhibit the recombination of photo­
generated electron-hole pairs and result in good photocatalytic
hydrogen production efficiency with the appear quantum yield of 38 %
at 420 nm. Obregon et al. [310] designed and constructed BiPO4/TiO2/
g-C3N4 ternary heterojunction catalyst, and realized the stepwise
transfer of photogenerated electrons and holes by using the energy band
difference of semiconductor (photogenerated electrons transfer along
the direction of g-C3N4→ TiO2→ BiPO4, photogenerated holes transfer
along the BiPO4→ TiO2→ g-C3N4 direction), which effectively improves
the efficiency of carrier separation. Dong et al. [311] constructed the
ZnO/ZnS/g-C3N4 ternary heterojunction catalyst with the “double Z-
type” carrier transport mechanism, it was reported that the synergistic
effect between the double Z-scheme interfaces significantly promoted
the charge carrier separation and remained good REDOX ability of the
electrons and holes, thus significantly improved the PHE performance of
the catalyst.

36
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 44. (a) and (b) are separately the TEM and HRTEM image of 19.3 %-NMS/SCN, (c) EDS element mapping images for C, N, Mo and S, (d) H2 evolution with 4 h of
illumination over the prepared samples, (e) SPV spectra of SCN, NMS and 19.3 %-NMS/SCN, (f) and (g) are separately the electrostatic potentials of SCN (0 0 1)
surface and NMS (0 0 2) surface, (h) is the schematic illustration for the photocatalytic mechanism over NMS/SCN S-scheme heterojunction. Adapted with permission
from ref [302]. Copyright by 2020 Elsevier.

7.3.2. g-C3N4/carbon heterostructure
As the most abundant element on Earth, carbon materials have
attracted great researches in the construction of g-C3N4-based hetero­
structure due to the merits of excellent conductivity, good stability, low
cost, good light absorption ability and various structure. Many carbon
materials, including C60 [312,313], carbon dots [314,315], graphene
[316], carbon nanotubes [317–319], amorphous carbon [320], and so
on, have been combined with g-C3N4 to construct the high active pho­
tocatalyst. Chai et al. [313] reported the high photocatalytic system by
decorating g-C3N4 with Fullerene. Li and coworkers [312] investigated
the interface effects of C60/g-C3N4 heterostructures on the electronic
properties, charge transfer and light absorption abilities based on the
first-principles calculations. They confirmed that the type-II band
alignment was formed between C60 and g-C3N4 provides main drive

Fig. 45. Schematic illustrating the mechanism of charge separation and photocatalytic processes on amorphous carbon/g-C3N4 hybrids under visible light irradi­
ation. Adapted with permission from ref [320]. Copyright by 2017 Elsevier.

37
D. Ma et al.
force for the transfer and separation of charge carriers. In addition, the
unsaturated N atoms included in the interfaces of g-C3N4 contributes
most in promoting the photocatalytic performance, while the saturated
nitrogen atoms lying in the interfaces will weaken the interfacial in­
teractions between C60 molecules and the g-C3N4 monolayers. Xu at al.
[320], fabricated the heterostructure by combing g-C3N4 with amor­
phous carbon, the photogenerated electrons tend to transfer from the CB
of g-C3N4 to amorphous carbon surface and thus facilitating the efficient
separation of photogenerated electrons and holes in g-C3N4 (Fig. 45). As
a result, the H2 evolution ability of the heterostructure can be increased
to 212.8 μmol/h/g, which was about 10 times higher than that of pure g-
C3N4.
7.3.3. g-C3N4/MOF heterostructure
As a kind of important functional materials, metal organic frame
works (MOFs) have also become a promising candidate in the con­
struction of heterostructure with g-C3N4 due to the merits of high spe­
cific surface area and adjustable pore structure [321–326]. From the
viewpoint of band structure, the CB of MOFs is consisted of the empty
outer orbitals of metal centers and the VB is mainly contributed by the
outer orbitals of organic linkers, thus, MOFs can also be excited by the
sunlight to generate electron-hole pairs and played the roles a semi­
conductor [327–335]. Pu et al. [330] fabricated 3D g-C3N4/Cu3P/UiO-
66 cubic structure by using a hydrothermal method. The fabricated
heterostructure displayed larger specific surface area of 1002.08 m2/g,
which was 23 times than that of g-C3N4. Moreover, the H2 evolution
activity of the sample was measured to be 79 μmol in 5 h, this can be
ascribed to that the MOF provides a large number of active sites and
surface areas for photocatalytic reaction. Arif et al. [334] combined the
g-C3N4-MoS2 heterostructure with ZnM-ZIF (Fig. 46), it was found that
the ZnM-ZIFs not only inhibited the aggregation of the g-C3N4-MoS2
heterostructure, but also improved the separation and transport effi­
ciency of charge carriers, and resulted in 214.4 and 3.7 times higher H2
evolution rate than that of g-C3N4 and g-C3N4-MoS2, respectively.
Zhao et al. [331] combined protonated g-C3N4 (p-g-C3N4) with Co-
MOF and introduced the Sm doping to constructed integrated 2D/2D
Fig. 46. (a) Scheme illustrating the synthesis of the ternary g-C3N4-MoS2-ZnNi-ZIF heterostructure. TEM images of the (b) g-C3N4, (c) ZnNi-ZIF (inset showing the
SEM image), (d) g-C3N4-MoS2-ZnNi-ZIF, (e) g-C3N4-MoS2, (f) g-C3N4-MoS2-ZnNi-ZIF, and (g) HRTEM image of the g-C3N4-MoS2-ZnNi-ZIF. (h) the photocatalytic
hydrogen production activity of the samples, (i) separation and utilization mechanism of the photogenerated charge carriers in the optimal g-C3N4-MoS2-ZnNi-ZIF.
Adapted with permission from ref [334]. Copyright by 2021 Royal Society of Chemistry.
38
Coordination Chemistry Reviews 500 (2024) 215489
dye-sensitized photocatalytic H2 evolution system. The protonated g-
C3N4 and Co-MOF directionally adsorb Eosin Y (EY) and triethanol­
amine (TEOA) molecules through hydrogen bond and complexation
separately and achieved a whole photocatalytic system. As shown in
Fig. 47a, the successful fabrication of the Sm doped heterostructure can
be confirmed from the change of color. Based on controlling the cate­
gory of inorganic protonic acids, the ratio of g-C3N4 to Co-MOF, the
doping amount of Sm, as well as the concentration of EY, the H2 evo­
lution ability of the 2D/2D heterostructure was optimized to be 73.42
μmol/h (Fig. 47b to i). It was found that the sensitizer (EY) and the
sacrificial agent (TEOA) were respectively coupled on the reduction site
(p-g-C3N4) and the oxidation site (2D Co-MOF) of the system and form
an integral dye-sensitized system, which realized the directional
migration of carriers and made full use of sensitizers and sacrificial
agents. In addition, the introduction of Sm in 2D Co-MOF has further
promoted the separation of photogenerated and transfer of electrons
(Fig. 47j).
Wang et al. [329] fabricated UiO-66/g-C3N4 (UG-x) heterostructure
through a thermal annealing process (Fig. 48a), the g-C3N4 was depos­
ited on the surface of UIO-66 and the deposition have no obvious effect
on the morphology of UIO-66 substrate (Fig. 48b to f). The photo­
catalytic activity of the hybrid can be controlled through the deposition
amount of g-C3N4, the highest H2 evolution was obtained over the UG-50
sample of 14.11 × 10− 6 mol/h, which is over 17 times higher than that
of g-C3N4 alone (Fig. 48g).
In addition, the charge transfer pathway in MOF/g-C3N4 hetero­
structures has also been discussed by other researchers [332–335]. In
this region, our group fabricated the 2D/2D heterostructure by
combining acidified boron-doped g-C3N4 (HBCNN) and cobalt
porphyrin metal organic frameworks (CoPMOF) together through a self-
assembly strategy [332]. It is found that a coordination connection has
formed between CoPMOF and HBCNN through Co-N bond, which forms
a pseudo-gap in the up-spin channel of electronic states, establishing an
electron-hole separation mechanism (Fig. 49a). The resultant HBCNN/
CoPMOF with optimum ratio exhibits a superior H2 evolution rate of
33.17 mmol/g/h, which is 3.04 and 100.50 times higher than the single
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 47. (a) photos of g-C3N4, p-g-C3N4, 2D Co-MOF, 2D Co-MOF/p-g-C3N4-50 % and 5 % Sm doped. The HER curves of (b) p-g-C3N4 protonated by different
inorganic protonic acids, (c) 2D Co-MOF/p-g-C3N4 with different contents of 2D Co-MOF, (d) composite materials with different Sm doping, (e) composite materials
with unprotonated g-C3N4, (f) composite materials with various rare earth element doping, the photocatalytic HER rates of 5 % Sm doped (g) in the solutions with
different concentration of EY, (h) in the different pH, (i) the photocatalytic stability tests of 5 % Sm doped in 20 h. Photocatalytic mechanism of 5 % Sm doped.
Adapted with permission from ref [331]. Copyright by 2020 Elsevier.

Fig. 48. (a) Schematic illustration of decorating g-C3N4 on UiO-66 octahedrons through annealing process. Increasing the g-C3N4 amount leads to higher coverage of
g-C3N4 on UiO-66 octahedrons. SEM images of (b) UiO-66, (c) UG-10 and (d) UG-50, (e) TEM image of UG-50, (f) EDS pattern of the g-C3N4, Zr signal comes from the
UiO-66, and Cu signal comes from the Cu grid, (g) The histogram showing the H2 production rate over UG- x samples (x = 10, 30, and 50). Adapted with permission
from ref [329]. Copyright by 2015 Wiley-VCH.

HBCNN and CoPMOF, respectively. Based on the detection of active
intermediate, the charge transfer between HBCNN and CoPMOF was
confirmed to be a Z-scheme pathway (Fig. 49b), which significantly
facilitates the transfer and separation of photogenerated charge carriers
and accelerates the photocatalytic reaction. Rajan et al. [335] reported a
type II energy transfer process between amorphous nickel-imidazole
MOF (aNi-MOF) and g-C3N4 (Fig. 49c), Zhang et al. [336] reported
the multi-sites sensitive photocatalytic mechanism in the MOF-5@g-
C3N4/NixMo1-xS2 heterostructure (Fig. 49d).

39
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 49. (a) Synthesis illustration of HBCNN/CoPMOF, (b) Schematic illustration of the possible heterojunction types of CoPMOF and HBCNN, Adapted with
permission from ref [332]. Copyright by 2022 Elsevier. (c) A mechanism for Type II heterojunction formation between aNi-MOF and g-C3N4, Adapted with
permission from ref [335]. Copyright by 2022 Elsevier. (d) Photocatalytic mechanism for H2 production of Nix-Mo1-xS2/MOF-5@g-C3N4 in EY sensitized under
visible light irradiation. Adapted with permission from ref [336]. Copyright by 2018 Elsevier.

7.3.4. g-C3N4-based homostructure
The raising of homojunction strategy is attractive in overcoming the
disadvantage of heterojunction in the formation of high-quality inter­
face. Composed by the same semiconductor materials, the same element
composition and similar crystal structure can minimize the lattice mis­
matches between semiconductors; at the same time, the difference in
positions of Fermi levels could induce band bending and form a build-in
electric field to inhibit the recombination and facilitate the separation of
photogenerated charge carriers [337–340]. Up to now, many efforts
have been devoted in the researches of g-C3N4-based homojunctions, the
π-π conjugate in triazine ring can be directly affected by the element
doping, molecular structure, as well as size and spatial structure of g-
C3N4. Thus, the homostructure can be constructed between the g-C3N4
semiconductors with different element doping, morphology and mo­
lecular structures [341–346]. For example, Liao et al. [341] constructed
p-n homojunction by combing nitrogen vacancies decorated g-C3N4
(NV-g-C3N4) with g-C3N4. Li et al. [346] reported the construction of O-
doped crystalline/non-crystalline g-C3N4 homojunction system. Inter­
estingly, the g-C3N4 with variety of spacial structures and energy band
structures can be form by carefully controlling the precursors and treat
temperatures and thus making the construction of homojunction easier
and controllable. Liu et al. [347] reported the fabrication of g-C3N4
based homojunction by treating the melamine precursor at different
temperatures. As shown in Fig. 50a, amorphous g-C3N4 (A600GCN) was
obtained at 600 ◦ C while crystalline g-C3N4 (CGCN) was gotten after
heating A600GCN at 750 ◦ C. Thus, the amorphous/crystalline g-C3N4
homojunction can be formed by treating CGCN in the presence of mel­
amine at 750 ◦ C. Li et al. [348] investigated the influence of tempera­
tures on the crystalline of g-C3N4 with the use of different precursors
(Fig. 50b). They found that the temperature of crystalline g-C3N4 formed
by melamine is up to 580 ◦ C, while that by cyanuric acid is 550 ◦ C. Based
on this attempt, they successfully obtained crystalline/non-crystalline
nano-homojunction samples by treating the precursors composed of
melamine and cyanuric acid at 550 ◦ C. Similarly, by using dicyandia­
mide and melamine as precursors and treating them at 600 ◦ C and
720 ◦ C respectively, Li et al. [349] fabricated the DCN (g-C3N4 fabri­
cated from dicyandiamide precursor) and MCN (g-C3N4 fabricated from
melamine precursor) with different energy band structures and thus
obtaining the DCN/MCN homojunction (Fig. 50c), which displayed
much higher H2 evolution ability than that of single catalyst due to the
formation of type II energy transfer pathway at the interface. Moreover,
the energy band structure of g-C3N4 also varies with their size and
morphology. Zheng et al. [350] fabricated 0D/1D g-C3N4 homojunction
through a facile in-situ thermal polymerization process by using the
melamine-cyanuric acid supramolecular and urea as co-precursor. As
shown in Fig. 50d, 0D g-C3N4 nanoparticles can be formed on the sur­
face of 1D g-C3N4 nanorods after the grind treatment.
Indeed, although it is facile and easy to construct g-C3N4 based
homojunction by controlling the calcination procedure and the type of
precursors, the limited types and forms of homogeneous junctions are
also a problem that needs to be solved. A widely adopted strategy is to
construct the homojunction by modifying partial of g-C3N4. For
example, coming from the same precursor urea and calcining with the
same procedures, Tang et al. [351] treated partial of the sample with
Poly (N,N-dimethyl acrylamide) to prepare the PDI-g-C3N4, which was
then treated together with another partial of g-C3N4 and thus obtaining
the PDI-g-C3N4/g-C3N4 (CPH) homojunction (Fig. 50e). Similarly, Feng
et al. [352] introduced a NaOH-assisted thermal polycondensation for
the preparation of N deficient g-C3N4, which was then combined with
pristine g-C3N4 and thus obtaining g-C3N4/g-C3N4-x homojunction

40
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 50. (a) Illustration of preparation process of A-CGCN composites. Adapted with permission from ref [347]. Copyright by 2018 The Royal Society of Chemistry.
(b) Schematic diagram for the formation of crystalline g-C3N4 and crystalline/ none-crystalline g-C3N4 nano-homojunction. Adapted with permission from ref [348].
Copyright by 2020 Elsevier. (c) Formation illustration of g-C3N4 layered homojunctions. Adapted with permission from ref [349]. Copyright by 2022 Elsevier. (d) The
schematic diagram of preparation process and photocatalytic test of MUCN. Adapted with permission from ref [350]. Copyright by 2021 Elsevier. (e) The synthesis
procedure of the g-C3N4/PDI-g-C3N4 homostructures. Adapted with permission from ref [351]. Copyright by 2021 Elsevier.

(Fig. 51). By controlling the ratio of g-C3N4-x to pristine g-C3N4, the
maximized utilization of light energy and photocatalytic activity can be
achieved due to the construction of balance between light absorption
and charge separation.
Our group [344] developed a homojunction by in situ decorating 2D
g-C3N4 (CN) with C-N compounds broken by s-triazine unit (BST), the
formation of CN/BST homojunction photocatalyst can be confirmed
from the AFM measurement (Fig. 52a and b). It was revealed that the
BST fragments tightly anchored on the CN NSs and act as electron-
trapping agents to rapidly transfer photogenerated electrons from the
CB of CN and thus efficiently inhibiting the recombination of photo­
generated electrons and holes (Fig. 52c). As a result, the optimized CN/
BST homojunction presents significantly enhanced photocatalytic H2
generation rate of 12.47 mmol/g/h, which was about 4 and 33 times
higher than that of pristine CN and BST, respectively.
By using melamine and thiourea as precursors and NH4Cl as soft-
template, Nong et al. [353] obtained the g-C3N4 with simultaneous
isotype heterojunction and porous structure by a thermal poly­
condensation method (Fig. 53a), which displayed superior photo­
catalytic ability compared to the traditional g-C3N4 catalyst (Fig. 53b). It
was found that the photogenerated e− and h+ can effectively diffuse to
the surface of the catalyst due to the efficient separation and charge
transfer resulted from the formation of the isotype heterojunction
structure, thus improving the photocatalytic efficiency (Fig. 53c).
Zeng et al. [340] fabricated a triazine g-C3N4/tri-straizine g-C3N4
homojunction. Tan et al. [354] constructed the homojunction by
combining meso-g-C3N4 with g-C3N4 NSs (Fig. 54a), the formed homo­
junction displayed much enhanced H2 evolution ability due to the
formation of type II energy transfer pathway between the two different
morphologies of g-C3N4. By depositing 2D sulfur-doped g-C3N4 NSs on
the surface of 3D g-C3N4 flower-like hierarchical structure (CN) through
the Van der Waals force, Xing et al. [355] constructed the 2D/3D g-C3N4
homostructure (Fig. 54b). The optimal photocatalytic H2 evolution of
2D/3D CNSCN reached up to 2196 μmol/g/h, which was 4.1 and 3.2
times higher than that of CN and CNS, respectively. Ma et al. [306] re­
ported the band alignment of 0D/2D homojunction by anchoring CN
quantum dots on g-C3N4 NSs (Fig. 54c), which displayed 8.6 times
higher H2 evolution ability than that of g-C3N4 NSs.
7.3.5. Single atoms decorated g-C3N4 heterostructure
Due to the special polymeric nature, g-C3N4 displays large specific
area and good flexibility, thus can be used as a matrix compatible with
various nanoparticles to prepare g-C3N4-supported composites. Espe­
cially, the sufficient regularly distributed N atoms in g-C3N4 served as
ideal anchoring centers to ensure the high dispersing of metal atoms,
which makes it possible for the prepare of single atom catalyst decorated
heterostructure system. Single atoms (SAs) modified g-C3N4 hetero­
structures have been recently gaining increasing attention due to the
outstanding PHE performance caused by the maximized efficiency of
metal atoms. Many SAs, such as Pd [356,357], Pt [358–360], Au [361],
Ni [362], Cu [363], Ru [364], Co [365], and Ag [366,367] atoms, have
been introduced into the 2D plane to improve the PHE ability of g-C3N4.
Wang et al. [367] constructed single atom Ag and carbon dots co-
decorated g-C3N4 catalyst. Zhu et al. [368] studied the size effect of Pt
on the PHE activity of g-C3N4, and they found that the size of Pt can be
controlled from single atoms to nano-clusters by the induced amount of

41
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 51. (a) Schematic illustration for the preparation of g-C3N4-x/g-C3N4 homojunction (left) and the corresponding photocatalytic activities of the samples (right).
(b) 3D charge density difference and corresponding planar averaged charge density difference for g-C3N4-x/g-C3N4. (c) Charge transfer and relative energy band
potential for g-C3N4-x/g-C3N4 homojunction. Adapted with permission from ref [352]. Copyright by 2023 Elsevier.

Fig. 52. (a) Two- and (b) three-dimensional AFM images of CN/BST-0.05, (c) Schematic diagram of the charge transfer mechanism of CN/BST-0.05. Adapted with
permission from ref [344]. Copyright by 2023 Royal Society of Chemistry.

Pt precursor. The single atom Pt modified g-C3N4 can be obtained with
about 0.1 wt% Pt loading amount, which displayed the highest PHE rate
of 473.82 µmol mg− 1 among the samples. The remarkably increased
photocatalytic ability was mainly attributed to the synergistic effect of
high light adsorption efficiency, effective charge separation, and highly
dispersed active sites of Pt atoms.
Ru is another widely studied metal in constructing SAs decorated g-
C3N4 system. As shown in Fig. 55a, Li and co-workers [364] prepared
micro-tailored porous g-C3N4 (t-CN) by H2O2 via a hydrothermal pro­
cess, and then Ru SAs were loaded on the surface to get Ru1-t-CN hy­
brids. The successful fabrication of SAs decorated sample was confirmed
by using the AC-SEM and XANES measurements (Fig. 55b to e). As a
result, the Ru SAs decorated t-CN displayed superior H2 evolution rate,
which was much higher than that of Ru nanoparticles decorated sample
(Fig. 55f). The authors thought that the most photo-introduced electrons
were concentratedly extracted into Ru-sites from the directional charge
transfer-channels at once. At the same time, the metal-support in­
teractions decreased the activation energy of reduction reaction, making
the Ru-sites act as preferential reactive sites to reducing H− to H2
(Fig. 55g). Zhang et al. [369] constructed phosphorus-coordinated Co
atom on g-C3N4 for overall water splitting, in which the anchored Co
single atom site is the active site for oxygen evolution reaction, while the
N atoms act as active sites for hydrogen evolution reaction.
Huang et al. [370] fabricated Ni SAs decorated g-C3N4 catalyst for
outstanding photocatalytic overall water splitting. It was found that the
utilization of a SA Ni-terminating agent to coordinate with the heptazine

42
D. Ma et al.
Fig. 53. (a) Formation of g-C3N4 with simultaneous isotype heterojunction and porous structure. (b) The first-order kinetics of the photocatalytic degradation
activity. (c) Photodegradation mechanism of the sample under visible light irradiation. Adapted with permission from ref [353]. Copyright by 2023 Springer.
moieties of g-C3N4 resulted in the formation of a new electronic orbital,
which is critical for optimizing photocatalysis associated with carbon
defects. The atomic and electronic structures and the band gap of g-C3N4
were adjusted by the new hybrid orbital. The SA Ni and the adjacent C
atom are recognized as the active sites for water oxidation and reduc­
tion, respectively, resulting in the efficient photocatalytic splitting of
water via a two-electron transfer pathway.
In addition, the interlayer SA decoration system was also reported.
Ren et al. [356] fabricated palladium SA coordinated cyano-group-rich
g-C3N4 (DN-UCN). Base on experiments and calculation, they claimed
that the special structure of DN-UCN nanosheets creates a physical
confinement environment for Pd atoms, while cyano groups serve as the
favorable anchoring sites for linking Pd atoms and DN-UCN via the Pd −
N coordination approach, thus guaranteeing the stabilization of isolated
Pd atoms in the interlayers of DN-UCN nanosheets (Fig. 56a). The co­
ordination of Pd atoms can modify the electronic structure and energy
band structure of g-C3N4 and create a built-in electric field to boost
charge-transfer dynamics. In addition, it was found that the charge
separation and transfer efficiency can be largely improved through the
Pd-N coordination bonds formed in the Pd-bridged interlayer channels,
thus boosting the photocatalytic H2 evolution activity (Fig. 56b).
Many researchers tried to give out explanation to the enhancement
of PHE ability on SAs decorated catalysts. Yang et al. [371] investigated
the regulating effect of Pt SAs on photocatalytic overall water splitting
performance of g-C3N4 based on energy band engineering by the spin-
polarized DFT calculations. It was found that the SA Pt resulted in
more positive VB of g-C3N4, thus the enhanced photo-response of the g-
C3N4 was due to the reduced in the band gap of the system rather than
the introduction of impurity levels (Fig. 57a), which was also reported
by others in the SA Pd decorated systems (Fig. 57b and c) [356,357]. In
addition, the free energy change of H adsorbed on the g-C3N4 was as
high as − 1.53 eV, while that of H adsorbed on the Pt SAs decorated g-
C3N4 was as low as 0.32 eV. This indicates that the PHE occurred on Pt
SAs decorated g-C3N4 is higher than that on the g-C3N4.
43
Coordination Chemistry Reviews 500 (2024) 215489
Zhai et al. [373] investigated the micro environment variation of Pt
SAs in affecting the defective levels of g-C3N4 and revealed the mecha­
nism of the promoted photocatalytic properties. Based on theoretic
calculation, they found that the charge redistribution of Pt SAs for Pt-
C2N is much greater than that of Pt-N2, indicating a stronger interaction
between the isolated Pt atoms and the lone-pair electrons of the neigh­
boring carbon/nitrogen atoms for Pt-C2N, which may be because that
the electronegativity of C atoms is lower than N atoms (Fig. 58a and d).
Thus, Pt SAs can act as a preferable active site to capture more electrons
during the photocatalytic process (Fig. 58c and d). In addition, the
correlation between the coordination environment of isolated atoms and
hydrogen evolution activity was also studied. As shown in Fig. 58e,
compared with Pt-N2 sites, Pt-C2N displays a suppressed Gibbs free en­
ergy (ΔG*) of (− 0.06 eV), indicating that the H* desorption barrier is
decreased, resulting in remarkably improved PHE activity for the Pt SAs
decorated sample. Focus on increasing the photocatalytic performance,
strong electronic interactions between the active metal sites and sur­
rounding atoms are critical [374,375]. Additionally, the local coordi­
nation environment of SAs has a significant influence on both its
electrical structure and catalytic behavior [376].
Similarly, Fang et al. [377] studied the H2 evolution ability of single
site Co-S anchored g-C3N4. As shown in Fig. 59a, in the fabrication of the
SAs decorated system, they firstly inserted single atom Co into the
structure of g-C3N4, and then the sample was vulcanized to prepare
composite Co-S single-site in g-C3N4. The formation of SAs decorated
sample can be confirmed from the TEM and element distribution map­
pings shown in Fig. 59b to d. As a result, the co-introduction of Co and S
single SAs displayed improved H2 evolution ability and good stability
(Fig. 59e to g). Base on theoretic calculation, it was found that the ab­
solute value of the standard Gibbs free energy of Co-S-CN (− 0.86 eV) is
much lower than that of CN (− 2.03 eV) (Fig. 59g), indicating that the
hydrogen evolution reaction occurs more easily on the Co-S-CN photo­
catalyst. Xu et al. [372] reported a much-improved PHE performance on
the SA Pd decorated g-C3N4, it was also demonstrated that the enhanced
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 54. (a) The formation procedure of meso-g-C3N4/g-C3N4 NSs laminated homojunction (left) and transfer path mechanism of photogenerated electron-hole in
meso-g-C3N4/g-g-C3N4 NSs laminated homojunction (right). Adapted with permission from ref [354]. Copyright by 2017 Elsevier. (b) and (c) are TEM images of
CNCNS, (d) Photocatalytic mechanism scheme of 2D/3D CNSCN homojunction. Adapted with permission from ref [355]. Copyright by 2022 Elsevier. (f)TEM image
of HJ-C3N4; (g) Magnified TEM image of HJ-C3N4 of region of (f) marked in red and a size distribution of CN QDs; (h) HRTEM image of CN QDs anchored in 2D g-
C3N4; (i)The estimated band structure of CN QDs and bare g-C3N4. Adapted with permission from ref [343]. Copyright by 2021 Elsevier.

photocatalytic activity is mainly due to the dramatically decreased
Gibbs free energy for atomic hydrogen adsorption onto the catalyst
surface.
It can be concluded that SAs have great potential for increasing the
PHE ability of g-C3N4, and the improved H2 evolution ability can be
ascribed to some typical merits brought by the introduction of SAs, such
as the improved light absorption capacity, charge transfer efficiency,
maximized atomic utilization, as well as electron conductivity. Most
importantly, the introduced SAs can efficiently decrease the Gibbs free
energy of H adsorbed on the g-C3N4, fundamentally improving the ki­
netics of photocatalytic reaction, which has been verified in many
photocatalytic reactions. At the same time, the strong interaction be­
tween the anchored SAs and the N atom in g-C3N4 guarantees the good
stability and long-life of hybrid system.
In summary, the construction of g-C3N4-based heterostructures and
homostructures are useful in obtaining improved the H2 evolution
ability due to the promoted charge transfer and utilization efficiency.
Some artful design, such as energy band structure manipulation, sur­
face/interface engineering, multiple-component heterostructures as
well as the selection of proper coupling material make it possible to
optimize the charge behavior and take the full advantages of each other
components. It is undoubted that some more smart design will be re­
ported in the exploration of high-performance g-C3N4-based photo­
catalyst to further promote the development of photocatalytic H2
evolution technology.
8. Conclusion and outlook
PHE from water splitting is a fantastic strategy to convert solar en­
ergy and water source into H2 energy, but the practical application of
this technology poses a great challenge to the development and design of
photocatalysts. g-C3N4-based photocatalysts are in the hotpot of PHE
field due to the merits of suitable energy band structure, good visible
light response ability, 2D planar character, good durability, easy to

44
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 55. (a) Illustration of preparation principle of Ru1-t-CN. (b) AC-STEM image of Ru1-t-CN. (c) The normalized XANES at the Ru K-edge. (d) The k2 -weighted FT-
EXAFS in R-space. (e) Ru K-edge EXAFS and curve-fft for Ru1-t-CN. (f) H2 evolution activity of the samples. (g) Catalytic mechanism illustration of Ru1-t-CN
photocatalyst. Adapted with permission from ref [364]. Copyright by 2022 Elsevier.

Fig. 56. (a) Top view, side view and of charge density distributions of DN-UCN and Pd/DN-UCN and the corresponding PDOS of each them. (b) Charge Separation
and Transfer as well as the mechanism for H2 Evolution in the 0.16%Pd/DN-UCN0.50 System under Full Solar Light Spectrum Irradiation. Adapted with permission
from ref [356]. Copyright by 2022 American Chemical Society.

45
D. Ma et al.
Fig. 57. (a) Diagram of band edge positions for the pristine monolayer g-C3N4 (left) and SA Pt decorated g-C3N4 (right). Adapted with permission from ref [371].
Copyright by 2021 Elsevier. (b) schematic illustration of the band gap structure of CN, Pd-CN, and Pdnano-CN. Adapted with permission from ref [372]. Copyright by
2021 Springer. (c) band structure alignments of various g-C3N4 and Pd/g-C3N4 samples. Adapted with permission from ref [356]. Copyright by 2022 American
Chemical Society.
fabrication and low cost. Focus on the basic properties, fabrication, and
modification in photocatalytic H2 evolution, this review presents a
comprehensive overview of g-C3N4-based photocatalysts. Despite the
significant advances have been made, the photocatalytic activity and
durability of g-C3N4-based photocatalysts are still far away to practical
applications. The design and construction of proper of photocatalysts
and the optimization of photocatalytic reaction system are in the crucial
needs to improve the photocatalytic performance and thus are worth
exploring in the future studies.
1) Self-modification is useful in changing the intrinsic electron struc­
ture and energy band position of g-C3N4, thus are expected to
improve the light absorption ability of photocatalyst and the
reduction capacity of photogenerated electrons, but it worth noting
that the self-modification procedure including doping and defect
engineering also bring inevitable negative effects such as charge
recombination and deep traps that induced by the unmanageable
doping level and defect distribution. Therefore, it is a technical task
in introducing impurities or defects into g-C3N4.
2) The construction of heterostructure is useful in realize complemen­
tary advantages but also faces some thorny problems, one of them is
the formation of contact interface, the traditional liquid fabrication
method usually introduce impurity while solid high temperature
calcination method is difficult to achieve uniform distribution of
different components, thus fail to form large area strong coupling
interface and result in limited photocatalytic performance
enhancement. In-situ strategy is promising in construct large area
intimate contacted interface between g-C3N4 and the second photo­
catalyst, but the utilization of in-situ strategy is only available in a
46
Coordination Chemistry Reviews 500 (2024) 215489
small kind of catalysts. In this point, researchers should take fully the
organic properties and morphology adjustability of g-C3N4 into
consideration and form chemical bonds link between g-C3N4 and the
second photocatalyst, so as to construct strong and stable interfacial
contact to promote the rapid migration and separation of carriers.
3) Some explanation to the movement of charge carriers and the pho­
tocatalytic mechanism are still disputable. For example, some
researcher thinks that shorter lifetime of photogenerated charge
carriers is good for photocatalytic reaction because of a faster charge
transmission speed, but some others believed that longer lifetime
meaning that the photogenerated charge carriers have more oppor­
tunity to transfer to the surface-active reaction sites before annihi­
lation. It is obvious that the photocatalytic performance is a
comprehensive result effected by multiple factors such as light ab­
sorption, charge transfer and surface reaction, more advanced
characterization methods, in-situ detection and theoretical calcula­
tion are expected to be used to further reveal the true face of pho­
tocatalytic reactions.
4) There is lack of an impeccable index and standard procedure to
compare fairly the photocatalytic hydrogen performance of various
g-C3N4-based photocatalysts in different photocatalytic system.
Despite the photocatalyst itself, the photocatalytic performance is
also seriously affected by the test procedure, such as the amount of
used photocatalyst in one reaction, the type and quantity of co-
catalysts and sacrificial reagents, reaction temperature, as well as
the intensity and wavelength of light sources, etc. All of these
mentioned factors are various in different literature, as a result, the
performance of photocatalytic hydrogen production is hardly com­
parable in different studies. Therefore, it is critically important to set
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

Fig. 58. Charge density difference of (a) Pt-C2N and (b) Pt-N2 (isosurface value = 0.005 Å-3), PDOS plots of (c) Pt-C2N and (d) Pt-N2, and (e) Gibbs free energies of
Pt-C2N and Pt-N2 Adapted with permission from ref [373]. Copyright by 2023 American Chemical Society.

Fig. 59. (a) Schematic diagram of the preparation of Co-S-C3N4. (b) TEM image and (c) HAADF-STEM image of Co-S-CN, and (d) is the corresponding elemental
mappings. (e) Photocatalytic hydrogen evolution performance of the as-prepared samples under visible light (λ > 400 nm). (f) Stability of photocatalytic hydrogen
evolution over CoS-CN. (g) The LSV curves and (h) the standard Gibbs free energy for the HER of CN and Co-S-CN. Adapted with permission from ref [377]. Copyright
by 2022 Elsevier.

proper standards to unify the photocatalytic performance tests and Declaration of Competing Interest
promote the development of g-C3N4-based photocatalytic H2
evolution. The authors declare that they have no known competing financial

47
D. Ma et al. Coordination Chemistry Reviews 500 (2024) 215489

interests or personal relationships that could have appeared to influence hydrogen evolution reaction under visible light, Energy Environ. Sci. 12 (2019)
2080–2147.
the work reported in this paper.
[22] G. Liao, Y. Gong, L. Zhang, H. Gao, G. Yang, B. Fang, Semiconductor polymeric
graphitic carbon nitride photocatalysts: the “holy grail” for the photocatalytic
Data availability hydrogen evolution reaction under visible light, Energy Environ. Sci. 12 (2019)
2080–2147.
[23] M. Rajeshwari, S. Kokilavani, S. Khan, Recent developments in architecturing the
Data will be made available on request. g-C3N4 based nanostructured photocatalysts: Synthesis, modifications and
applications in water treatment, Chemosphere 291 (2022), 132735.
[24] J.V. Liebig, About some nitrogen compounds, Ann. Pharm. (Poznan) 10 (10)
Acknowledgements (1834) 15.
[25] E. Franklin, The ammono carbonic acids, J. Am. Chem. Soc. 44 (1922) 486–509.
This work was sponsored by the National Natural Science Founda­ [26] L. Pauling, J. Sturdivant, The Structure of cyameluric acid, hydromelonic acid
and related substances, PNAS 23 (1937) 615–620.
tion of China (21972110), the Postdoctoral Science Foundation of China [27] R. Hosmane, M. Rossman, N. Leonard, Synthesis and structure of Tri-s-Triazine,
(2021M692535), the Natural Science Foundation of Shaanxi Province J. Am. Chem. Soc. 104 (1982) 5497–5499.
(2022JQ-095), and the Youth Foundation of State Key Laboratory of [28] M.L. Cohen, Predicting useful materials, Science 261 (1993) 307–308.
[29] Y. Wang, Q. Jiang, J. Shang, X. Xie, Y. Li, Advances in the Synthesis of
Electrical Insulation and Power Equipment (EIPE2131).
Mesoporous Carbon Nitride Materials, Acta Phys. -Chim. Sin. 32 (8) (2016)
1913–1928.
Appendix A. Supplementary data [30] F. Goettmann, A. Fischer, M. Antonietti, A. Thomas, Metal free catalysis of
sustainable Friedel-Crafts reactions: direct activation of benzene by narbon
nitrides to avoid the use of metal chlorides and halogenated compounds, Chem.
Supplementary data to this article can be found online at https://doi. Commun. 4530–4532 (2006).
org/10.1016/j.ccr.2023.215489. [31] X. Wang, K. Maeda, A. Thomas, K. Takanabe, G. Xin, J. Carlsson, K. Domen,
M. Antonietti, A metal-free polymeric photocatalyst for hydrogen production
from water under visible light, Nat. Mater. 8 (2009) 76–80.
References [32] E. Kroke, M. Schwarz, E. Horath-Bordon, P. Kroll, B. Noll, A. Norman, Tri-s-
triazine derivatives. Part I. from trichloro-tri-s-triazine to graphitic C3N4
structures, New J. Chem. 26 (2002) 508–512.
[1] S. Koohi-Fayegh, M.A. Rosen, A review of energy storage types, applications and
[33] W. Liu, S. Xu, S. Guan, R. Liang, M. Wei, D. Evans, X. Duan, Confined synthesis of
recent developments, J. Energy Storage 27 (2020), 101047.
carbon nitride in a layered host matrix with unprecedented solid-state quantum
[2] B.E. Lebrouhi, J.J. Djoupo, B. Lamrani, K. Benabdelaziz, T. Kousksou, Global
yield and stability, Adv. Mater. 30 (2018) 1704376.
hydrogen development - A technological and geopolitical overview, Int. J.
[34] S. Cao, J. Low, J. Yu, M. Jaroniec, Polymeric photocatalysts based on graphitic
Hydrogen Energy 47 (2022) 7016–7048.
carbon nitride, Adv. Mater. 27 (2015) 2150–2176.
[3] C. Tarhan, M.A. Çil, A study on hydrogen, the clean energy of the future:
[35] W. Wang, C. Zhou, Y. Yang, G. Zeng, C. Zhang, Y. Zhou, J. Yang, D. Huang,
Hydrogen storage methods, J. Energy Storage 40 (2021), 102676.
H. Wang, W. Xiong, X. Li, Y. Fu, Z. Wang, Q. He, M. Jia, H. Luo, Carbon nitride
[4] T.J. Whittemore, C. Xue, J. Huang, J.C. Gallucci, C. Turro, Single-chromophore
based photocatalysts for solar photocatalytic disinfection, can we go further?
single-molecule photocatalyst for the production of dihydrogen using low-energy
Chem. Eng. J. 404 (2021), 126540.
light, Nature Chem. 12 (2020) 180–185.
[36] X. Wang, S. Blechert, M. Antonietti, Polymeric graphitic carbon nitride for
[5] C. Li, D. Zhu, S. Cheng, Y. Zuo, Y. Wang, C. Ma, H. Dong, Recent research
heterogeneous photocatalysis, ACS Catal. 2 (2012) 1596–1606.
progress of bimetallic phosphides-based nanomaterials as cocatalyst for
[37] T. Sano, S. Tsutsui, K. Koike, T. Hirakawa, Y. Teramoto, N. Negishi, K. Takeuchi,
photocatalytic hydrogen evolution, Chin. Chem. Lett. 33 (2022) 1141–1153.
Activation of graphitic carbon nitride (g-C3N4) by alkaline hydrothermal
[6] X. Xu, X. Tian, B. Sun, Z. Liang, H. Cui, J. Tian, M. Shao, 1T-phase molybdenum
treatment for photocatalytic NO oxidation in gas phase, J. Mater. Chem. A 1
sulfide nanodots enable efficient electrocatalytic nitrogen fixation under ambient
(2013) 6489–6496.
conditions, Appl. Catal. B Environ. 272 (2020), 118984.
[38] Y. Zhao, J. Zhang, L. Qu, Graphitic carbon nitride/ graphene hybrids as new
[7] W. Liu, Y. Wan, Y. Xiong, P. Gao, Green hydrogen standard in China: Standard
active materials for energy conversion and storage, ChemNanoMat 1 (2015)
and evaluation of low-carbon hydrogen, clean hydrogen, and renewable
298–318.
hydrogen, Int. J. Hydrogen Energy 47 (2022) 24584–24591.
[39] A. Zambon, J. Mouesca, C. Gheorghiu, P. Bayle, J. Pecaut, M. Claeys-Bruno,
[8] M. Ramadan, A review on coupling Green sources to Green storage (G2G): Case
S. Gambarelli, L. Dubois, S-heptazine oligomers: promising structural models for
study on solar-hydrogen coupling, Int. J. Hydrogen Energy 46 (2021)
graphitic carbon nitride, Chem. Sci. 7 (2016) 945–950.
30547–30558.
[40] B. Lotsch, M. Dçblinger, J. Sehnert, L. Seyfarth, J. Senker, O. Oeckler, W. Schnick,
[9] Gasunie. What is hydrogen and how is it made? [EB/OL]. [2020-12-26].
Unmasking melon by a complementary approach employing electron diffraction,
https://www.theworldofhydrogen.com/gasunie/what-is-hydrogen/.
solid-state NMR spectroscopy, and theoretical calculations-structural
[10] R. Gao, Q. Ge, N. Jiang, H. Cong, M. Liu, Y. Zhang, Graphitic carbon nitride (g-
characterization of a carbon nitride polymer, Chem. Eur. J. 13 (2007)
C3N4))-based photocatalytic materials for hydrogen evolution, Front. Chem.
4969–4980.
(2022), 1048504.
[41] K. Maeda, X. Wang, Y. Nishihara, D. Lu, M. Antonietti, K. Domen, Photocatalytic
[11] H. Zhang, J. Liu, L. Jiang, Photocatalytic hydrogen evolution based on carbon
activities of graphitic carbon nitride powder for water reduction and oxidation
nitride and organic semiconductors, Nanotechnol. 33 (2022), 322001.
under visible light, J. Phys. Chem. C 113 (2009) 4940–4947.
[12] C. Li, H. Wu, D. Zhu, T. Zhou, M. Yan, G. Chen, J. Sun, G. Dai, F. Ge, H. Dong,
[42] W. Ho, Z. Zhang, M. Xu, X. Zhang, X. Wang, Y. Huang, Enhanced visible light-
High-efficient charge separation driven directionally by pyridine rings grafted on
driven photocatalytic removal of NO: effect on layer distortion on g-C3N4 by H2
carbon nitride edge for boosting photocatalytic hydrogen evolution, Appl. Catal.
heating, Appl. Catal. B Environ. 179 (2015) 106–112.
B Environ. 297 (2021), 120433.
[43] J. Wang, D. Hao, J. Ye, N. Umezawa, Determination of crystal structure of
[13] Z. Liang, S. Yang, X. Wang, H. Cui, X. Wang, J. Tian, The metallic 1T-phase WS2
graphitic carbon nitride: ab lnitio evolutionary search and experimental
nanosheets as cocatalysts for enhancing the photocatalytic hydrogen evolution of
validation, Chem. Mater. 29 (2017) 2694–2707.
g-C3N4 nanotubes, Appl. Catal. B Environ. 274 (2020), 119114.
[44] W. Wang, M. Chen, D. Huang, G. Zeng, C. Zhang, C. Lai, C. Zhou, Y. Yang,
[14] A. Fujishima, K. Honda, Electrochemical photolysis of water at a semiconductor
M. Cheng, L. Hu, W. Xiong, Z. Li, Z. Wang, An overview on nitride and nitrogen
electrode, Nature 238 (1972) 37–38.
doped photocatalysts for energy and environmental applications, Compos. B Eng.
[15] J. Fu, J. Yu, C. Jiang, B. Cheng, g-C3N4-based heterostructured photocatalysts,
172 (2019) 704–723.
Adv. Energy Mater. 8 (2018) 1701503.
[45] S. Sun, S. Liang, Recent advances in functional mesoporous graphitic carbon
[16] C. Kranz, M. Wachtler, Characterizing photocatalysts for water splitting: from
nitride (mpg-C3N4) polymers, Nanoscale 9 (2017) 10544–10578.
atoms to bulk and from slow to ultrafast processes, Chem. Soc. Rev. 50 (2021)
[46] B. Zhu, L. Zhang, B. Cheng, J. Yu, First-principle calculation study of tri-s-triazine-
1407–1437.
based g-C3N4: a review, Appl. Catal., B 224 (2018) 983–999.
[17] Y. Gao, W. Nie, X. Wang, F. Fan, C. Li, Advanced space- and time-resolved
[47] Z. Zhang, Y. Zhang, L. Lu, Y. Si, S. Zhang, Y. Chen, K. Dai, P. Duan, L. Duan, J. Liu,
techniques for photocatalyst studies, Chem. Commun. 56 (2020) 1007–1021.
Graphitic carbon nitride nanosheet for photocatalytic hydrogen production: the
[18] J. Zhu, S. Pang, T. Dittrich, Y. Gao, W. Nie, J. Cui, R. Chen, H. An, F. Fan, C. Li,
impact of morphology and element composition, Appl. Surf. Sci. 391 (2017)
Visualizing the nano cocatalyst aligned electric fields on single photocatalyst
369–375.
particles, Nano Lett. 17 (2017) 6735–6741.
[48] B. Zhu, J. Zhang, C. Jiang, B. Cheng, J. Yu, First principle investigation of halogen
[19] W. Ong, L. Tan, Y. Ng, S. Yong, S. Chai, Graphitic carbon nitride (g-C3N4)-based
doped monolayer g-C3N4 photocatalyst, Appl. Catal., B 207 (2017) 27–34.
photocatalysts for artificial photosynthesis and environmental remediation: Are
[49] J. Cui, S. Liang, X. Wang, J. Zhang, First principle modeling of oxygen-doped
we a step closer to achieving sustainability? Chem. Rev. 116 (2016) 7159–7329.
monolayer graphitic carbon nitride, Mater. Chem. Phys. 161 (2015) 194–200.
[20] T. Zhou, P. Zhang, D. Zhu, S. Cheng, H. Dong, Y. Wang, G. Che, Y. Niu, M. Yan,
[50] S. Yan, S. Li, G. Zou, Photodegradation performance of g-C3N4 fabricated by
C. Li, Synergistic effect triggered by skeleton delocalization and edge induction of
directly heating melamine, Langmuir 25 (2009) 10397–10401.
carbon nitride expedites photocatalytic hydrogen evolution, Chem. Eng. J. 442
[51] G. Zhang, J. Zhang, M. Zhang, X. Wang, Polycondensation of thiourea into carbon
(2022), 136190.
nitride semiconductors as visible light photocatalysts, J. Mater. Chem. 22 (2012)
[21] G. Liao, Y. Gong, L. Zhang, H. Gao, G. Yang, B. Fang, Semiconductor polymeric
8083–8091.
graphitic carbon nitride photocatalysts: the ‘‘holy grail’’ for the photocatalytic

48
D. Ma et al.
[52] Q. Deng, Q. Li, Facile preparation of Mg-doped graphitic carbon nitride
composites as a solid base catalyst for Knoevenagel condensations, J. Mater. Sci.
53 (2018) 506–515.
[53] P. Niu, L. Yin, Y. Yang, G. Liu, H. Cheng, Increasing the visible light absorption of
graphitic carbon nitride (melon) photocatalysts by homogeneous self-
modification with nitrogen vacancies, Adv. Mater. 26 (2014) 8046–8052.
[54] Q. Tay, P. Kanhere, C. Ng, S. Chen, S. Chakraborty, A. Huan, T. Sum, Ahuja, R.
Z. Chen, Defect engineered g-C3N4 for efficient visible light photocatalytic
hydrogen production, Chem. Mater. 27 (2015) 4930–4933.
[55] F. Dong, Z. Wang, Y. Sun, W. Ho, H. Zhang, Engineering the nanoarchitecture and
texture of polymeric carbon nitride semiconductor for enhanced visible light
photocatalytic activity, J. Colloid Interface Sci. 401 (2013) 70–79.
[56] P. Niu, L. Zhang, G. Liu, H. Cheng, Graphene-like carbon nitride nanosheets for
improved photocatalytic activities, Adv. Funct. Mater. 22 (2012) 4763–4770.
[57] J. Xu, L. Zhang, R. Shi, Y. Zhu, Chemical exfoliation of graphitic carbon nitride for
efficient heterogeneous photocatalysis, J. Mater. Chem. A 1 (2013) 14766–14772.
[58] F. Fina, S. Callear, G. Carins, J. Irvine, Structural investigation of graphitic carbon
nitride via XRD and neutron diffraction, Chem. Mater. 27 (2015) 2612–2618.
[59] H. Yan, Y. Chen, S. Xu, Synthesis of graphitic carbon nitride by directly heating
sulfuric acid treated melamine for enhanced photocatalytic H2 production from
water under visible light, Int. J. Hydrogen Energy 37 (2012) 125–133.
[60] Y. Zhong, Z. Wang, J. Feng, S. Yan, H. Zhang, Z. Li, Z. Zou, Improvement in
photocatalytic H2 evolution over g-C3N4 prepared from protonated melamine,
Appl. Surf. Sci. 295 (2014) 253–259.
[61] X. Zhang, J. Hu, H. Jiang, Facile modification of a graphitic carbon nitride
catalyst to improve its photoreactivity under visible light irradiation, Chem. Eng.
J. 256 (2014) 230–237.
[62] G. Dong, L. Zhang, Porous structure dependent photo reactivity of graphitic
carbon nitride under visible light, J. Mater. Chem. 22 (2012) 1160–1166.
[63] A. Sudhaika, P. Raizadaa, P. Shandilyaa, D. Jeongb, J. Lim, P. Singh, Review on
fabrication of graphitic carbon nitride based efficient nanocomposites for
photodegradation of aqueous phase organic pollutants, J. Ind. Eng. Chem. 67
(2018) 28–51.
[64] F. Zhang, G. Tang, J. Xu, C. Li, Solvothermal preparation and tribological
performance of g-C3N4/TiO2 hybridsas oil-based lubricant additives, Micro. Nano
Lett. 14 (2019) 1355–1360.
[65] H. Montigaud, B. Tanguy, G. Demazeau, I. Alves, S. Courjault, C3N4: dream or
reality? solvothermal synthesis as macroscopic samples of the C3N4 graphitic
form, J. Mater. Sci. 35 (2000) 2547–2552.
[66] Y. Cui, Z. Ding, X. Fu, X. Wang, Construction of conjugated carbon nitride
nanoarchitectures in solution at low temperatures for photoredox catalysis,
Angew. Chem. Int. Ed. 124 (47) (2012) 11984–11988.
[67] T. Sekine, H. Kanda, Y. Bando, M. Yokoyama, K. Hojou, A graphitic carbon
nitride, J. Mater. Sci. Lett. 9 (1990) 1376–1378.
[68] I. Alves, G. Demazeau, B. Tanguy, F. Weill, On a new model of the graphitic form
of C3N4, Solid State Commun. 109 (1999) 697–701.
[69] X. Cao, M. Deng, B. Tang, Y. Ding, X. Yang, Development of photocatalytic chip
seal for nitric oxide removal on thesurface of pavement using g-C3N4/TiO2
composite, Road Mater. Pavement Design 22 (2021) 1178–1194.
[70] K. Xiao, P. Giusto, L. Wen, L. Jiang, M. Antonietti, Nanofluidic ion transport and
energy conversion through ultrathin free-standing polymeric carbon nitride
membranes, Angew. Chem. Int. Ed. 57 (2018) 10123–10126.
[71] Z. Gao, Y. Qu, X. Zhou, L. Wang, Y. Song, P. Schmuki, Pt-decorated g-C3N4/TiO2
nanotube arrays with enhanced visible-light photocatalytic activity for H2
evolution, Chemistryopen 5 (2016) 197–200.
[72] R. Liu, Y. Bie, Y. Qiao, T. Liu, Y. Song, Design of g-C3N4/TiO2 nanotubes
heterojunction for enhanced organic pollutants degradation in waste water,
Mater. Lett. 251 (2019) 126–130.
[73] L. Cui, S. Liu, F. Wang, J. Li, Y. Song, Y. Sheng, H. Zou, Growth of uniform g-C3N4
shells on 1D TiO2 nanofibers via vapor deposition approach with enhanced visible
light photocatalytic activity, J. Alloys. Compounds 826 (2020), 154001.
[74] Q. Lu, J. Deng, Y. Hou, H. Wang, H. Li, Y. Zhang, One-step electrochemical
synthesis of ultrathin graphitic carbon nitride nanosheets and their application to
the detection of uric acid, Chem. Commun. 51 (2015) 12251–12253.
[75] T. Zhao, Q. Zhou, Y. Lv, D. Han, K. Wu, L. Zhao, L. Zhao, Y. Shen, S. Liu, Y. Zhang,
Ultrafast condensation of carbon nitride on electrodes with exceptional boosted
photocurrent and electrochemiluminescence, Angew. Chem. Int. Ed. 132 (2019)
1155–1159.
[76] W. Liu, N. Iwasab, S. Fujitab, H. Koizumib, M. Yamaguchic, T. Shimada, Porous
graphitic carbon nitride nanoplates obtained by a combined exfoliation strategy
for enhanced visible light photocatalytic activity, Appl. Surf. Sci. 499 (2020),
143901.
[77] N. Rono, J. Kibet, B. Martincigh, V. Nyamori, A comparative study between
thermal etching and liquid exfoliation of bulk graphitic carbon nitride to
nanosheets for the photocatalytic degradation of a model environmental
pollutant, rhodamine b, J. Mater. Sci. - Mater. Electron. 32 (2021) 687–706.
[78] M. Nasir, G. Yang, I. Ayub, S. Wang, L. Wang, X. Wang, W. Yan, S. Peng,
S. Ramakarishna, Recent development in graphitic carbon nitride based
photocatalysis for hydrogen generation, Appl. Catal., B, 257 (2019).
[79] P. Wu, J. Wang, J. Zhao, L. Guo, F.E. Osterloh, High alkalinity boosts visible light
driven H2 evolution activity of g-C3N4 in aqueous methanol, Chem. Commun. 50
(2014) 15521–15524.
[80] Q. Wang, T. Hisatomi, Q. Jia, H. Tokudome, M. Zhao, C. Wang, Scalable water
splitting on particulate photocatalyst sheets with a solar-to-hydrogen energy
conversion efficiency exceeding 1%, Nat. Mat. 15 (6) (2016) 611–615.
49
Coordination Chemistry Reviews 500 (2024) 215489
[81] C. Wang, X. Yi, C. Wang, Powerful combination of MOFs and C3N4 for enhanced
photocatalytic performance, Appl. Catal., B 247 (2019) 24–48.
[82] G. Liao, C. Li, X. Li, B. Fang, Emerging polymeric carbon nitride Z-scheme systems
for photocatalysis, Cell Rep. Phys. Sci. 2 (2021), 100355.
[83] Y. Yu, W. Yan, X. Wang, P. Li, W. Gao, H. Zou, S. Wu, K. Ding, Surface engineering
for extremely enhanced charge separation and photocatalytic hydrogen evolution
on g-C3N4, Adv. Mater. 30 (2018) 1705060.
[84] M. Khan, F. Zhang, M. Osada, S. Mao, S. Shen, Graphitic carbon nitride-based
low-dimensional heterostructures for photocatalytic applications, Sol. RRL 4
(2020) 1900435.
[85] Y. Li, M. Zhou, B. Cheng, Y. Shao, Recent advances in g-C3N4-based
heterojunction photocatalysts, J. Mater. Sci. Technol. 56 (2020) 1–17.
[86] J. Zhang, X. An, N. Lin, W. Wu, L. Wang, Z. Li, R. Wang, Y. Wang, J. Liu, M. Wu,
Engineering monomer structure of carbon nitride for the effective and mild photo
oxidation reaction, Carbon 100 (2016) 450–455.
[87] J. Zhang, G. Zhang, X. Chen, S. Lin, L. Mohlmann, G. Dolega, G. Lipner,
M. Antonietti, S. Blechert, X. Wang, Co monomer control of carbon nitride
semiconductors to optimize hydrogen evolution with visible light, Angew. Chem.
Int. Ed. 51 (2012) 3183–3187.
[88] P. Xia, M. Liu, B. Cheng, J. Yu, L. Zhang, Dopamine modified g-C3N4 and its
enhanced visible-light photocatalytic H2–production activity, ACS Sustain. Chem.
Eng. 6 (2018) 8945–8953.
[89] W. Che, W. Cheng, T. Yao, F. Tang, W. Liu, H. Su, Y. Huang, Q. Liu, J. Liu, F. Hu,
Z. Pan, Z. Sun, Z.S. Wei, Fast photoelectron transfer in (cring)-C3N4 plane
heterostructural nanosheets for overall water splitting, J. Am. Chem. Soc. 139
(2017) 3021–3026.
[90] Z. Li, S. Zhou, Q. Yang, Z. Zhang, X. Fang, Insight into the enhanced hydrogen
evolution activity of 2,4-diaminopyrimidine doped graphitic carbon nitride
photocatalysts, J. Phys. Chem. C 123 (2019) 2228–2237.
[91] S. Li, W. Si, L. Cui, L. Shi, Improved photocatalytic H2 evolution performance of
mesoporous graphitic carbon nitride with cyano-group, Diamond Relat. Mater.
110 (2020), 108149.
[92] S. Tang, Y. Xu, W. Zhang, Embedding thiophene-amide into g-C3N4 skeleton with
induction and delocalization effects for high photocatalytic H2 evolution,
Catalysts 12 (2022) 1043.
[93] S. Wang, C. Wan, F. Chen, M. Chong, D. Cheng, Regulating the bandgap of
graphitic carbon nitride via Mn doping for boosting visible-light-driven water
reduction, J. Phys. D: Appl. Phys. 5 (2022), 284002.
[94] X. Wu, F. Chen, X. Wang, H. Yu, In situ one-step hydrothermal synthesis of
oxygen-containing groups-modified g-C3N4 for the improved photocatalytic H2-
evolution performance, Appl. Surf. Sci. 427 (2018) 645–653.
[95] J. Zhang, X. Chen, K. Takanabe, K. Maeda, K. Domen, J. Epping, X. Fu,
M. Antonietti, X. Wang, Synthesis of a carbon nitride structure for visible-light
catalysis by copolymerization, Angew. Chem., Int. Ed. 49 (2010) 441–444.
[96] L. Zhou, K. Hu, T. Dong, Q. Wang, H. Huang, C. Lu, J. Kou, Z. Xu, Carbon ring and
molecular scaffold co-doped g-C3N4 heterostructural nanosheets for highly
efficient hydrogen evolution, Mater. Res. Bull. 144 (2021), 111482.
[97] Y. Jiao, J. Qin, Y. Li, J. Wang, Z. He, Z. Li, Nitrobenzene inarched carbon nitride
nanotube drives efficient directional carriers separation for superior
photocatalytic hydrogen production, J. Colloid Interface Sci. 616 (2022)
691–700.
[98] J. Zhang, G. Zhang, X. Chen, S. Lin, L. Moehlmann, G. Dolega, G. Lipner,
M. Antonietti, S. Blechert, X. Wang, Co-monomer control of carbon nitride
semiconductors to optimize hydrogen evolution with visible light, Angew. Chem.
Int. Ed. 51 (2012) 3183–3187.
[99] J. Zhang, M. Zhang, S. Lin, X. Fu, X. Wang, Molecular doping of carbon nitride
photocatalysts with tunable bandgap and enhanced activity, J. Catal. 310 (2014)
24–30.
[100] H. Zheng, J. Zhang, X. Wang, X. Fu, Modification of carbon nitride photocatalysts
by copolymerization with diaminomaleonitrile, Acta Phys. Chim. Sin. 28 (2012)
2336–2342.
[101] J. Jiang, S. Cao, C. Hu, C. Chen, A comparison study of alkali metal-doped g-C3N4
for visible-light photocatalytic hydrogen evolution, Chin. J. Catal. 38 (2017)
1981–1989.
[102] X. Yan, Z. Jia, H. Che, S. Chen, P. Hu, J. Wang, L. Wang, A selective ion
replacement strategy for the synthesis of copper doped carbon nitride nanotubes
with improved photocatalytic hydrogen evolution, Appl. Catal., B 234 (2018)
19–25.
[103] D. Yang, X. Sun, H. Dong, X. Zhang, H. Tang, J. Sheng, J. Wei, F. Zhang,
Improvement of the photocatalytic hydrogen production activity of g-C3N4 by
doping selenides as cocatalysts, Mater. Sci. Semicond. Process. 85 (2018) 76–82.
[104] N. Wang, J. Wang, J. Hu, X. Lu, J. Sun, F. Shi, Z. Liu, Z. Lei, R. Jiang, Design of
palladium-doped g-C3N4 for enhanced photocatalytic activity toward hydrogen
evolution reaction, ACS Appl. Energy Mater. 1 (2018) 2866–2873.
[105] T. Chen, D. Yin, F. Zhao, K. Kyu, B. Liu, D. Chen, K. Huang, L. Deng, L. Li,
Fabrication of 2D heterojunction photocatalyst Co-g-C3N4/MoS2 with enhanced
solar-light-driven photocatalytic activity, New J. Chem. 43 (2019) 463–473.
[106] Y. Wang, S. Zhao, Y. Zhang, J. Fang, Y. Zhou, S. Yuan, C. Zhang, W. Chen, One-pot
synthesis of K-doped g-C3N4 nanosheets with enhanced photocatalytic hydrogen
production under visible-light irradiation, Appl. Surf. Sci. 440 (2018) 258–265.
[107] S. Hu, F. Li, Z. Fan, F. Wang, Y. Zhao, Z. Lv, Band gap-tunable potassium doped
graphitic carbon nitride with enhanced mineralization ability, Dalton Trans. 44
(2015) 1084–1092.
[108] Y. Wang, Y. Zhang, S. Zhao, Z. Huang, W. Chen, Y. Zhou, X. Lv, S. Yuan, Bio-
template synthesis of Mo-doped polymer carbon nitride for photocatalytic
hydrogen evolution, Appl. Catal., B 248 (2019) 44–53.
D. Ma et al.
[109] S. Sun, J. Li, J. Cui, X. Gou, Q. Yang, Y. Jiang, S. Liang, Z. Yang, Simultaneously
engineering K-doping and exfoliation into graphitic carbon nitride (g-C3N4) for
enhanced photocatalytic hydrogen production, Int. J. Hydrogen Energy 44 (2019)
778–787.
[110] X. Yang, Z. Tian, Y. Chen, H. Huang, J. Hu, B. Wen, In situ synthesis of 2D
ultrathin cobalt doped g-C3N4 nanosheets enhances photocatalytic performance
by accelerating charge transfer, J. Alloys Compd. 859 (2021), 157754.
[111] Y. Jiang, Z. Lin, Y. Zhang, Y. Lai, D. Liang, C. Yang, Facile synthesis of porous C-
doped C3N4: fast charge separation and enhanced photocatalytic hydrogen
evolution, New J. Chem. 44 (2020) 17891–17898.
[112] S. Sun, J. Li, J. Cui, X. Gou, Q. Yang, S. Liang, Z. Yang, J, Zhang, Constructing
oxygen-doped g-C3N4 nanosheets with an enlarged conductive band edge for
enhanced visible-light-driven hydrogen evolution, Inorg. Chem. Front. 5 (2018)
1721–1727.
[113] H. Wang, B. Wang, Y. Bian, L. Dai, Enhancing photocatalytic activity of graphitic
carbon nitride by codoping with p and c for efficient hydrogen generation, ACS
Appl. Mater. Interfaces 9 (2017) 21730–21737.
[114] J. Li, X. Liu, C. Liu, H. Che, C. Li, Facile nitrogen and sulfur deficient engineering
on sulfur doped g-C3N4 for efficiently photocatalytic H2 evolution, J. Taiwan Inst.
Chem. Eng. 117 (2020) 93–102.
[115] S. Guo, Y. Tang, Y. Xie, C. Tian, Q. Feng, W. Zhou, B. Jiang, P-doped tubular g-
C3N4 with surface carbon defects: universal synthesis and enhanced visible-light
photocatalytic hydrogen production, Appl. Catal., B 218 (2017) 664–671.
[116] M. Mohamed, M. Zain, L. Minggu, M. Kassim, J. Jaafar, N. Amin, Z. Hir,
M. Rosmi, Enhancement of visible light photocatalytic hydrogen evolution by bio-
mimetic C-doped graphitic carbon nitride, Int. J. Hydrogen Energy 44 (2019)
13098–13105.
[117] H. Guo, Z. Shu, D. Chen, Y. Tan, J. Zhou, F. Meng, T. Li, One-step synthesis of s-
doped g-C3N4 nanosheets for improved visible-light photocatalytic hydrogen
evolution, Chem. Phys. 533 (2020), 110714.
[118] C. Wang, C. Yang, J. Qin, S. Rajendran, X. Zhang, A facile template synthesis of
phosphorus-doped graphitic carbon nitride hollow structures with high
photocatalytic hydrogen production activity, Mater. Chem. Phys. 275 (2022),
125299.
[119] Z. Zhao, Z. Shu, J. Zhou, W. Wang, T. Li, J. Chen, Facile one-pot synthesis of C, O-
codoped nano-structured g-C3N4 with superior photocatalytic hydrogen
evolution, Mater. Res. Bull. 145 (2022), 111565.
[120] B. Yan, G. Yang, Enhancing electron density of bulk g-C3N4 through phosphorus
doping for promoting photocatalytic hydrogen evolution reaction, Appl. Surf. Sci.
570 (2021), 151186.
[121] P. Xiao, D. Jiang, T. Liu, D. Li, M. Chen, Facile synthesis of carbon-doped g-C3N4
for enhanced photocatalytic hydrogen evolution under visible light, Mater. Lett.
212 (2018) 111–113.
[122] X. Wang, B. Liu, X. Xiao, S. Wang, W. Huang, Boron dopant simultaneously
achieving nanostructure control and electronic structure tuning of graphitic
carbon nitride with enhanced photocatalytic activity, J. Mater. Chem. C 9 (2021)
14876–14884.
[123] X. Xia, C. Xie, B. Xu, X. Ji, G. Gao, P. Yang, Role of B-doping in g-C3N4 nanosheets
for enhanced photocatalytic NO removal and H2 generation, J. Ind. Eng. Chem.
105 (2022) 303–312.
[124] C. Yang, S. Zhang, Y. Huang, K. Lv, S. Fang, X. Wu, Q. Li, J. Fan, Sharply
increasing the visible photoreactivity of g-C3N4 by breaking the intralayered
hydrogen bonds, Appl. Surf. Sci. 505 (2020), 144654.
[125] J. Ran, T. Ma, G. Gao, X. Du, S. Qiao, Porous p-doped graphitic carbon nitride
nanosheets for synergistically enhanced visible-light photocatalytic H2
production, Energy Environ. Sci. 8 (2015) 3708–3717.
[126] D. Zhao, Y. Wang, C. Dong, Y. Huang, J. Chen, F. Xue, S. Shen, L. Guo, Boron-
doped nitrogen-deficient carbon nitride-based Z-scheme heterostructures for
photocatalytic overall water splitting, Nature Energy 6 (2021) 388–397.
[127] Y. Li, S. Zhu, Y. Liang, Z. Li, S. Wu, C. Chang, S. Luo, Z. Cui, One-step synthesis of
Mo and S co-doped porous g-C3N4 nanosheets for efficient visible-light
photocatalytic hydrogen evolution, Appl. Surf. Sci. 536 (2021), 147743.
[128] W. Fang, J. Liu, L. Yu, Z. Jiang, W. Shangguan, Novel (Na,O) co-doped g-C3N4
with simultaneously enhanced absorption and narrowed bandgap for highly
effificient hydrogen evolution, Appl. Catal., B 209 (2017) 631–636.
[129] Y. Si, Y. Zhang, L. Lu, S. Zhang, Y. Chen, J. Liu, H. Jin, S. Hou, K. Dai, W. Song,
Boosting visible light photocatalytic hydrogen evolution of graphitic carbon
nitride via enhancing it interfacial redox activity with cobalt/nitrogen doped
tubular graphitic carbon, Appl. Catal., B 225 (2018) 512–518.
[130] H. Wei, Y. Zhang, G. Zhang, J. Cui, Y. Wang, Y. Qin, X. Zhang, H. Tan, J. Liu,
Y. Wu, In situ W/O co-doped hollow carbon nitride tubular structures with
enhanced visible-light-driven photocatalytic performance for hydrogen evolution,
Int. J. Hydrogen Energy 46 (2021) 234–246.
[131] L. Chen, D. Zhu, J. Li, X. Wang, J. Zhu, P. Francisc, Y. Zheng, Sulfur and potassium
co-doped graphitic carbon nitride for highly enhanced photocatalytic hydrogen
evolution, Appl. Catal. B 273 (2020), 119050.
[132] X. Bai, M. Li, J. Li, X. Rao, S. Zheng, Y. Zhang, Graphitic carbon nitride codoped
with sulfur and yttrium for efficient visible-light photocatalytic performance, ACS
Appl. Energy Mater. 4 (2021) 14390–14399.
[133] Z. Zhao, Z. Shu, J. Zhou, W. Wang, T. Li, Jieyu Chen, Facile one-pot synthesis of C,
O-codoped nano-structured g-C3N4 with superior photocatalytic hydrogen
evolution, Mater. Res. Bull. 145 (2022), 111565.
[134] H. Tang, Z. Xia, R. Chen, Q. Liu, T. Zhou, Oxygen doped g-C3N4 with nitrogen
vacancy for enhanced photocatalytic hydrogen evolution, Asian J. Chem. 15
(2020) 3456–3461.
50
Coordination Chemistry Reviews 500 (2024) 215489
[135] C. Sua, Y. Zhou, L. Zhang, X. Yu, S. Gao, X. Sun, C. Cheng, Q. Liu, J. Yang,
Enhanced n→π* electron transition of porous P-doped g-C3N4 nanosheets for
improved photocatalytic H2 evolution performance, J. Mater. Chem. C 9 (2021)
14876–14884.
[136] C. Han, P. Su, B. Tan, X. Ma, H. Lv, C. Huang, P. Wang, Z. Tong, G. Li, Y. Huang,
Z. Liu, Defective ultra-thin two-dimensional g-C3N4 photocatalyst for enhanced
photocatalytic H2 evolution activity, J. Colloid Interface Sci. 581 (2021) 159–166.
[137] F. Su, Z. Wang, H. Xie, Y. Zhang, C. Ding, L. Ye, Structural distortion of g-C3N4
induced by n-defects for enhanced photocatalytic hydrogen evolution, Catalysts
12 (2022) 1496.
[138] R. Mo, J. Li, Y. Tang, H. Li, J. Zhong, Introduction of nitrogen defects into a
graphitic carbon nitride framework by selenium vapor treatment for enhanced
photocatalytic hydrogen production, Appl. Surf. Sci. 476 (2019) 552–559.
[139] Q. Liang, Z. Li, Z. Huang, F. Kang, Q. Yang, Holey graphitic carbon nitride
nanosheets with carbon vacancies for highly improved photocatalytic hydrogen
production, Adv. Funct. Mater. 25 (2015) 6885–6892.
[140] H. Yu, R. Shi, Y. Zhao, T. Bian, Y. Zhao, C. Zhou, G. Waterhouse, Z. Wu, C. Tung,
T. Zhang, Alkali-assisted synthesis of nitrogen deficient graphitic carbon nitride
with tunable band structures for efficient visible-light-driven hydrogen evolution,
Adv. Mater. 29 (2017) 1605148.
[141] X. Liu, L. Gao, G. Qi, J. Zhang, B. Li, Y. Chen, Enhanced visible light
photocatalytic water-splitting activity over LaVO4/g-C3N4 with oxygen defects,
New J. Chem. 45 (2021) 18615–18622.
[142] Y. Wang, S. Zhao, Y. Zhang, J. Fang, W. Chen, S. Yuan, Y. Zhou, Facile synthesis of
self-assembled g-C3N4 with abundant nitrogen defects for photocatalytic
hydrogen evolution, ACS Sustain. Chem. Eng. 6 (2018) 10200–10210.
[143] C. Xu, W. Zhang, Facile synthesis of nitrogen deficient g-C3N4 by
copolymerization of urea and formamide for efficient photocatalytic hydrogen
evolution, Mol. Catal. 453 (2018) 85–92.
[144] J. Huang, Y. Cao, H. Wang, H. Yu, F. Peng, H. Zou, Z. Liu, Revealing active-site
structure of porous nitrogen-defected carbon nitride for highly effective
photocatalytic hydrogen evolution, Chem. Eng. J. 373 (2019) 687–699.
[145] G. Dong, Y. Wen, H. Fan, C. Wang, Z. Cheng, M. Zhang, J. Ma, S, Zhang, Graphitic
carbon nitride with thermally-induced nitrogen defects: an effiffifficient process
to enhance photocatalytic H2 production performance, RSC Adv. 10 (2020)
18632–18638.
[146] G. Xu, J. Shen, S. Chen, Y. Gao, H. Zhang, J. Zhang, Double defects modified
carbon nitride nanosheets with enhanced photocatalytic hydrogen evolution,
Phys. Chem. Chem. Phys. 20 (2018) 17471–17476.
[147] C. Yang, Z. Xue, J. Qin, M. Sawangphrukc, X. Zhang, R. Liu, Heterogeneous
structural defects to prompt charge shuttle in g-C3N4 plane for boosting visible-
light photocatalytic activity, Appl. Catal., B 259 (2019), 118094.
[148] M. Tan, C. Yu, J. Li, Y. Li, C. Tao, C. Liu, H. Meng, Y. Su, L. Qiao, Y. Bai,
Engineering of g-C3N4-based photocatalysts to enhance hydrogen evolution, Adv.
Colloid Interface Sci. 295 (2021), 102488.
[149] S. Zhai, P. Guo, J. Zheng, P. Zhao, B. Suo, Y. Wan, Density functional theory study
on the stability, electronic structure and absorption spectrum of small size g-C3N4
quantum dots, Comput. Mater. Sci. 148 (2018) 149–156.
[150] X. Dai, Z. Han, H. Fan, S. Ai, Sulfur doped carbon nitride quantum dots with
efficient fluorescent property and their application for bioimaging, J. Nanopart
Res 20 (2018) 315.
[151] H. Wang, Q. Lu, M. Li, H. Li, Y. Liu, H. Li, Y. Zhang, S. Yao, Electrochemically
prepared oxygen and sulfur co-doped graphitic carbon nitride quantum dots for
fluorescence determination of copper and silver ions and biothiols, Anal. Chim.
Acta 1027 (2018) 121–129.
[152] W. Wang, J. Yu, Z. Shen, D. Chan, T. Gu, g-C3N4 quantum dots: direct synthesis,
upconversion properties and photocatalytic application, Chem. Commun. 50
(2014) 10148–10150.
[153] C. Zheng, X. Qiu, J. Han, Y. Wu, S. Lin, Zero-dimensional-g-CNQD -coordinated
two-dimensional porphyrin MOF hybrids for boosting photocatalytic CO2
reduction, ACS Appl. Mat. Interfaces 11 (2019) 42243–42249.
[154] M. Chen, M. Li, S. Lee, X. Zhao, S. Lin, Constructing novel graphitic carbon
nitride-based nanocomposites - from the perspective of material dimensions and
interfacial characteristics, Chemosphere 302 (2022), 134889.
[155] B. Zhou, M. Waqas, B. Yang, K. Xiao, S. Wang, C. Zhu, J. Li, J. Zhang, Convenient
one-step fabrication and morphology evolution of thin-shelled honeycomb-like
structured g-C3N4 to significantly enhance photocatalytic hydrogen evolution,
Appl. Surf. Sci. 506 (2020), 145004.
[156] Y. Zeng, X. Liu, C. Liu, L. Wang, Y. Xia, S. Zhang, S. Luo, Y. Pei, Scalable one-step
production of porous oxygen-doped g-C3N4 nanorods with effective electron
separation for excellent visible-light photocatalytic activity, Appl. Catal., B 224
(2018) 1–9.
[157] X. Liu, S. Xu, H. Chi, T. Xu, Y. Guo, Y. Yuan, B. Yang, Ultrafifine 1D graphene
interlayer in g-C3N4/graphene/recycled carbon fiber heterostructure for
enhanced photocatalytic hydrogen generation, Chem. Eng. J. 359 (2019)
1352–1359.
[158] X. Bai, L. Wang, R. Zong, Y. Zhu, Photocatalytic activity enhanced via g-C3N4
nanoplates to nanorods, J. Phys. Chem. C 117 (2013) 9952–9961.
[159] Z. You, Y. Su, Y. Yu, H. Wang, T. Qin, F. Zhang, Q. Shen, H. Yang, Preparation of
g-C3N4 nanorod/InVO4 hollow sphere composite with enhanced visible-light
photocatalytic activities, Appl. Catal., B 213 (2017) 127–135.
[160] Y. Zheng, L. Lin, X. Ye, F. Guo, X. Wang, Helical graphitic carbon nitrides with
photocatalytic and optical activities, Angew. Chem. Int. Ed. 53 (2014)
11926–11930.
[161] B. Liu, L. Ye, R. Wang, J. Yang, Y. Zhang, R. Guan, L. Tian, X. Chen, Phosphorus-
doped graphitic carbon nitride nanotubes with amino-rich surface for efficient
D. Ma et al.
CO2 capture, enhanced photocatalytic activity, and product selectivity, ACS Appl.
Mat. Interfaces 10 (2018) 4001–4009.
[162] M. Li, L. Zhang, X. Fan, M. Wu, M. Wang, R. Cheng, L. Zhang, H. Yao, J. Shi, Core-
shell LaPO4/g-C3N4 nanowires for highly active and selective CO2 reduction,
Appl. Catal., B. 201 (2017) 629–635.
[163] B. Palanivel, M. Shkir, T. Alshahrani, A. Mani, Novel NiFe2O4 deposited S-doped
g-C3N4 nanorod: visible-light-driven heterojunction for photo-Fenton like
tetracycline degradation, Diamond Relat. Mater. 112 (2021), 108148.
[164] Q. Liang, Z. Li, Y. Bai, Z. Huang, F. Kang, Q. Yang, Reduced-sized monolayer
carbon nitride nanosheets for highly improved photoresponse for cell imaging
and photocatalysis, Sci. China Mater. 60 (2017) 109–118.
[165] Y. Yuan, Z. Shen, S. Wu, Y. Su, L. Pei, Z. Jia, M. Ding, W. Bai, Y. Chen, Z. Yu,
Z. Zou, Liquid exfoliation of g-C3N4 nanosheets to construct 2D–2D MoS2/g-C3N4
photocatalyst for enhanced photocatalytic H2 production activity, Appl. Catal., B
246 (2019) 120–128.
[166] Y. Li, R. Jin, Y. Xing, J. Li, S. Song, X. Liu, M. Li, R. Jin, Macroscopic foam-like
holey ultrathin g-C3N4 nanosheets for drastic improvement of visible-light
photocatalytic activity, Adv. Energy Mater. 6 (2016) 1601273.
[167] J. Fu, C. Bie, B. Cheng, C. Jiang, J. Yu, Hollow cosx polyhedrons act as high-
efficiency cocatalyst for enhancing the photocatalytic hydrogen generation of g-
C3N4, ACS Sustain. Chem. Eng. 6 (2018) 2767–2779.
[168] R. Shen, J. Xie, H. Zhang, A. Zhang, X. Chen, X. Li, Enhanced solar fuel H2
generation over g-C3N4 nanosheet photocatalysts by the synergetic effect of noble
metal-free Co2P cocatalyst and the environmental phosphorylation strategy, ACS
Sustain. Chem. Eng. 6 (2018) 816–826.
[169] Y. Li, M. Gu, X. Zhang, J. Fan, K. Lv, S. Carabineiro, F. Dong, 2D g-C3N4 for
advancement of photogenerated carrier dynamics: status and challenges, Mater.
Today 41 (2020) 270–303.
[170] Q. Han, B. Wang, J. Gao, Z. Cheng, Y. Zhao, Z. Zhang, L. Qu, Atomically thin
mesoporous nanomesh of graphitic C3N4 for high-efficiency photocatalytic
hydrogen evolution, ACS Nano 10 (2016) 2745–2751.
[171] X. Zhang, X. Yuan, L. Jiang, J. Zhang, H. Yu, H. Wang, G. Zeng, Powerful
combination of 2D g-C3N4 and 2D nanomaterials for photocatalysis: Recent
advances, Chem. Eng. J. 390 (2020), 124475.
[172] J. Yi, T. Fei, L. Li, Q. Yu, S. Zhang, Y. Song, J. Lian, X. Zhu, J. Deng, H. X, H. Li,
Large-scale production of ultrathin carbon nitride-based photocatalysts for high-
yield hydrogen evolution, Appl. Catal., B 281 (2021), 119475.
[173] M. Zhu, C. Zhai, M. Sun, Y. Hu, B. Yan, Y. Du, Ultrathin graphitic C3N4 nanosheet
as a promising visible-light-activated support for boosting photoelectrocatalytic
methanol oxidation, Appl. Catal., B 203 (2017) 108–115.
[174] Q. Lin, L. Li, S. Liang, M. Liu, J. Bi, L. Wu, Efficient synthesis of monolayer carbon
nitride 2D nanosheet with tunable concentration and enhanced visible-light
photocatalytic activities, Appl. Catal., B 163 (2015) 135–142.
[175] R. Du, B. Li, X. Han, K. Xiao, X. Wang, C. Zhang, J. Arbiol, A. Cabot, 2D/2D
heterojunction of TiO2 nanoparticles and ultrathin g-C3N4 nanosheets for efficient
photocatalytic hydrogen evolution, Nanomaterials 12 (2022) 1557.
[176] X. Ma, B. Luo, Z. Zeng, S. Hu, D. Jing, Significantly enhanced photocatalytic
hydrogen generation over a 2D/2D Z-Scheme La2NiO4/g-C3N4 hybrid free of
noble metal cocatalyst, ACS Appl. Energy Mater. 4 (2021) 10721–10730.
[177] P. Lv, F. Duan, J. Sheng, S. Lu, H. Zhu, M. Du, M. Chen, The 2D/2D p-n
heterojunction of ZnCoMOF/g-C3N4 with enhanced photocatalytic hydrogen
evolution under visible light irradiation, Appl. Organomet Chem. 35 (2021)
e6124.
[178] L. Fang, Y. Li, P. Liu, D. Wang, H. Zeng, X. Wang, H. Yang, Facile Fabrication of
large-aspect-ratio g-C3N4 nanosheets for enhanced photocatalytic hydrogen
evolution, ACS Sustain Chem. Eng. 5 (2017) 2039–2043.
[179] H. Dong, M. Xiao, D. Zhu, Y. Zuo, S. Cheng, Z. Han, C. Li, CoCO3 hierarchical
structure embedded on g-C3N4 nanosheets to assemble 3D/2D Z-scheme
heterojunction towards efficiently and stably photocatalytic hydrogen
production, Int. J. Hydrogen Energy 46 (2021) 32044–32054.
[180] Q. Fan, J. Liu, Y. Yu, S. Zuo, A template induced method to synthesize nanoporous
graphitic carbon nitride with enhanced photocatalytic activity under visible light,
RSC Adv. 4 (2014) 61877–61883.
[181] Z. Huang, Y. Zhang, H. Dai, Y. Wang, C. Qin, W. Chen, Y. Zhou, S. Yuan, Highly
dispersed Pd nanoparticles hybridizing with 3D hollow-sphere g-C3N4 to
construct 0D/3D composites for efficient photocatalytic hydrogen evolution,
J. Catal. 378 (2019) 331–340.
[182] W. Luo, X. Chen, Z. Wei, D. Liu, W. Yao, Y. Zhu, Three-dimensional network
structure assembled by g-C3N4 nanorods for improving visible-light
photocatalytic performance, Appl. Catal., B 255 (2019), 117761.
[183] Z. Chen, S. Lu, Q. Wu, F. He, N. Zhao, C. He, C. Shi, Salt-assisted synthesis of 3D
open porous g-C3N4 decorated with cyano groups for photocatalytic hydrogen
evolution, Nanoscale 10 (2018) 3008.
[184] W. Li, X. Chu, F. Wang, Y. Dang, X. Liu, X. Wang, C. Wang, Enhanced cocatalyst-
support interaction and promoted electron transfer of 3D porous g-C3N4/GO-M
(Au, Pd, Pt) composite catalysts for hydrogen evolution, Appl. Catal., B 288
(2021), 120034.
[185] B. Jiang, H. Huang, W. Gong, X. Gu, T. Liu, J. Zhang, W. Qin, H. Chen, Y. Jin,
Z. Liang, L. Jiang, Wood-inspired binder enabled vertical 3D printing of g-C3N4/
CNT arrays for highly efficient photoelectrochemical hydrogen evolution, Adv.
Funct. Mater. 31 (2021) 2105045.
[186] X. Qian, X. Meng, J. Sun, L. Jiang, Y. Wang, J. Zhang, X. Hu, M. Shalom, J. Zhu,
Salt-Assisted synthesis of 3D porous g-C3N4 as a bifunctional photo and
electrocatalyst, ACS Appl. Mater. Interfaces 11 (2019) 27226–27232.
51
Coordination Chemistry Reviews 500 (2024) 215489
[187] X. Chen, R. Shi, Q. Chen, Z. Zhang, W. Jiang, Y. Zhu, T. Zhang, Three-dimensional
porous g-C3N4 for highly efficient photocatalytic overall water splitting, Nano
Energy 59 (2019) 644–650.
[188] Y. Wang, M. Liu, F. Fan, G. Li, J. Duan, Y. Li, G. Jiang, W. Yao, Enhanced full-
spectrum photocatalytic activity of 3D carbon-coated C3N4 nanowires via giant
interfacial electric field, Appl. Catal., B 318 (2022), 121829.
[189] J. Khamrai, I. Ghosh, A. Savateev, M. Antonietti, B. Koenig, Photo-Ni-dual-
catalytic C(sp2)-C(sp3) cross-coupling reactions with mesoporous graphitic carbon
nitride as a heterogeneous organic semiconductor photocatalyst, ACS Catal. 10
(2020) 3526–3532.
[190] W. Wu, Z. Ruan, J. Li, Y. Li, Y. Jiang, X. Xu, D. Li, Y. Yuan, K. Lin, In situ
preparation and analysis of bimetal co-doped mesoporous graphitic carbon
nitride with enhanced photocatalytic activity, Micro Nano Lett. 11 (2019) 10.
[191] C. Cheng, J. Shi, L. Wen, C. Dong, Y. Huang, Y. Zhang, S. Zong, Z. Diao, S. Shen,
L. Guo, Disordered nitrogen-defect-rich porous carbon nitride photocatalyst for
highly efficient H2 evolution under visible-light irradiation, Carbon 181 (2021)
193–203.
[192] X. She, L. Liu, H. Ji, Z. Mo, Y. Li, L. Huang, D. Du, H. Xu, H. Li, Template-free
synthesis of 2D porous ultrathin nonmetal-doped g-C3N4 nanosheets with highly
efficient photocatalytic H2 evolution from water under visible light, Appl. Catal.,
B 187 (2016) 144–153.
[193] Y. Zhang, Z. Huang, C.i. Dong, J. Shi, C. Cheng, X. Guan, S. Zong, B. Luo,
Z. Cheng, D. Wei, Y. Huang, S. Shen, L. Guo, Synergistic effect of nitrogen vacancy
on ultrathin graphitic carbon nitride porous nanosheets for highly efficient
photocatalytic H2 evolution, Chem. Eng. J. 431 (2022).
[194] Y. Zou, J. Shi, D. Ma, Z. Fan, L. Cheng, D. Sun, Z. Wang, C. Niu, WS2/graphitic
carbon nitride heterojunction nanosheets decorated with CdS quantum dots for
photocatalytic hydrogen production, ChemSusChem 11 (2018) 1187–1197.
[195] H. Che, C. Liu, G. Che, G. Liao, H. Dong, C. Li, N. Song, C. Li, Facile construction
of porous intramolecular g-C3N4-based donor-acceptor conjugated copolymers as
highly efficient photocatalysts for superior H2 evolution, Nano Energy 67 (2020),
104273.
[196] M. Wu, Y. Gong, T. Nie, J. Zhang, R. Wang, H. Wang, B. He, Template-free
synthesis of nanocage-like g-C3N4 with high surface area and nitrogen defects for
enhanced photocatalytic H2 activity, J. Mater. Chem. A 7 (2019) 5324–5332.
[197] S. Zhang, S. Song, P. Gu, R. Ma, D. Wei, G. Zhao, T. Wen, R. Jehan, B. Hu,
X. Wang, Visible-light-driven activation of persulfate over cyano and hydroxyl
group co-modifified mesoporous g-C3N4 for boosting bisphenol A degradation,
J. Mater. Chem. A 7 (2019) 5552–5560.
[198] W. Chen, M. Liu, X. Li, L. Mao, Synthesis of 3D mesoporous g-C3N4 for efficient
overall water splitting under a Z-scheme photocatalytic system, Applied Surface
Science 512 (2020), 145782.
[199] X. Li, A.F. Masters, T. Maschmeyer, Photocatalytic hydrogen evolution from
silica-templated polymeric graphitic carbon nitride-Is the surface area important,
ChemCatChem 7 (2015) 121–126.
[200] G.P. Mane, S.N. Talapaneni, C. Anand, S. Varghese, H. Iwai, Q. Ji, K. Ariga,
T. Mori, A. Vinu, Preparation of highly ordered nitrogen-containing mesoporous
carbon from a gelatin biomolecule and its excellent sensing of acetic acid, Adv.
Funct. Mater. 22 (2012) 3596–3604.
[201] A. Fihri, M. Bouhrara, U. Patil, D. Cha, Y. Saih, V. Polshettiwar, Fibrous nano-
silica supported ruthenium (KCC-1/Ru): A sustainable catalyst for the
hydrogenolysis of alkanes with good catalytic activity and lifetime, ACS Catal. 2
(2012) 1425–1431.
[202] V. Polshettiwar, D. Cha, X. Zhang, J.M. Basset, High surface-area silica
nanospheres (KCC-1) with a fibrous morphology, Angew. Chem. Int. Ed. 49
(2010) 9652–9656.
[203] Z. Huang, F. Li, B. Chen, T. Lu, Y. Yuan, G. Yuan, Well-dispersed g-C3N4
nanophases in mesoporous silica channels and their catalytic activity for carbon
dioxide activation and conversion, Appl. Catal., B (2013), 136–137, 269–277.
[204] Y. Jun, W. Hong, M. Antonietti, A. Thomas, Mesoporous, 2D hexagonal carbon
nitride and titanium nitride/ carbon composites, Adv. Mater. 21 (2009)
4270–4274.
[205] J. Wang, C. Zhang, Y. Shen, Z. Zhou, J. Yu, Y. Li, W. Wei, S. Liu, Y. Zhang,
Environment-friendly preparation of porous graphite-phase polymeric carbon
nitride using calcium carbonate as templates, and enhanced photoelectrochemical
activity, J. Mater. Chem. A 3 (2015) 5126–5131.
[206] X. Chen, H. Wang, R. Meng, M. Chen, Porous graphitic carbon nitride synthesized
via using carbon nanotube as a novel recyclable hard template for efficient visible
light photocatalytic organic pollutant degradation, ChemistrySelect 4 (2019)
6123–6129.
[207] Z. Li, J. He, H. Ma, L. Zang, D. Li, S. Guo, Y. Ci, Preparation of heterogeneous
TiO2/g-C3N4 with a layered mosaic stack structure by use of montmorillonite as a
hard template approach: TC degradation, kinetic, mechanism, pathway and DFT
investigation, Appl. Clay Sci. 207 (2021), 106107.
[208] F. He, G. Chen, Y. Yu, Y. Zhou, Y. Zheng, S. Hao, The sulfur bubble template-
mediated synthesis of uniform porous g-C3N4 with superior photocatalytic
performance, Chem. Commun. 51 (2015) 425e7.
[209] H. Yan, Soft-templating synthesis of mesoporous graphitic carbon nitride with
enhanced photocatalytic H2 evolution under visible light, Chem Commun. 48
(2012) 3430e2.
[210] P. Deng, W. Hong, Z. Cheng, L. Zhang, Y. Hou, Facile fabrication of nickel/porous
g-C3N4 by using carbon dot as template for enhanced photocatalytic hydrogen
production, Int. J. Hydrogen Energy 45 (2022) 33543–33551.
[211] M.S. Akple, J. Low, S. Wageh, A.A. Al-Ghamdi, J. Yu, J. Zhang, Enhanced visible
light photocatalytic H2-production of g-C3N4/WS2 composite heterostructures,
Appl. Surf. Sci. 358 (2015) 196–203.
D. Ma et al.
[212] G. Zhang, Z. Lan, L. Lin, S. Lin, X. Wang, Overall water splitting by Pt/g-C3N4
photocatalysts without using sacrificial agents, Chem. Sci. 7 (5) (2016)
3062–3066.
[213] H. Yu, P. Xiao, P. Wang, J. Yu, Amorphous molybdenum sulfide as highly efficient
electron-cocatalyst for enhanced photocatalytic H2 evolution, Appl. Catal., B 193
(2016) 217–225.
[214] J. Dong, Y. Shi, C. Huang, Q. Wu, T. Zeng, W. Yao, A New and stable Mo-Mo2C
modified g-C3N4 photocatalyst for efficient visible light photocatalytic H2
production, Appl. Catal., B 243 (2019) 27–35.
[215] Q. Zhu, Z. Xu, B. Qiu, M. Xing, J. Zhang, Emerging cocatalysts on g-C3N4 for
photocatalytic hydrogen evolution, Small 17 (2021) 2101070.
[216] Z. Guo, Y. Zhao, H. Shi, X. Yuan, W. Zhen, L. He, H. Che, C. Xue, J. Mu, MoSe2/g-
C3N4 heterojunction coupled with Pt nanoparticles for enhanced photocatalytic
hydrogen evolution, J. Phys. Chem. Solids 156 (2021), 110137.
[217] W. Hu, J. Zhang, J. Tian, Y. Dang, W. Wang, H. Zhan, B. Ma, Greatly enhanced
photocatalytic hydrogen production on CdS/(Pt/g-C3N4) via dual functions of Pt
on semiconductors interface, Int. J. Hydrogen Energy 47 (2022) 29295–29304.
[218] W. Zhao, L. Xie, M. Zhang, Z. Ai, H. Xi, Y. Li, Q. Shi, J. Chen, Enhanced
photocatalytic activity of all-solid-state g-C3N4/Au/P25 Z-scheme system for
visible-light-driven H2 evolution, Int. J. Hydrogen Energy 41 (2016) 6277–6287.
[219] L. Hong, H. Xu, Y. Zhu, Z. Li, B. Bai, G. Ding, Surface plasmon resonance
enhanced hydrogen evolution from water with graphitic carbon nitride
photocatalyst, Catal. Lett. (2022), https://doi.org/10.1007/s10562-022-04168-z.
[220] J. Zeng, T. Song, M. Lv, T. Wang, J. Qin, H. Zeng, Plasmonic photocatalyst Au/g-
C3N4/NiFe2O4 nanocomposites for enhanced visible-light-driven photocatalytic
hydrogen evolution, RSC Adv. 6 (2016) 54964–54975.
[221] Y. Chen, X. Ren, X. Wang, Z. Tian, X. Yang, J. Lu, H. Bai, T. Jiao, H. Huang, J. Hu,
Construction of Ag decorated P-doped g-C3N4 nanosheets Schottky junction via
silver mirror reaction for enhanced photocatalytic activities, Int. J. Hydrogen
Energy 47 (2022) 250–263.
[222] T. Ren, Y. Dang, Y. Xiao, H.u. Qi, D. Deng, J. Chen, P. He, Depositing Ag
nanoparticles on g-C3N4 by facile silver mirror reaction for enhanced
photocatalytic hydrogen production, Inorg. Chem. Commun. 123 (2021), 108367.
[223] Y. Yang, C. Lu, J. Ren, X. Li, Y. Ma, W. Huang, X. Zhao, Enhanced photocatalytic
hydrogen evolution over TiO2/g-C3N4 2D heterojunction coupled with plasmon
Ag nanoparticles, Ceram. Int. 46 (2020) 5725–5732.
[224] B. Lin, Y. Zhou, B. Xu, C. Zhu, W. Tang, Y. Niu, J. Di, P. Song, J. Zhou, X. Luo,
L. Kang, R. Duan, Q. Fu, H. Liu, R. Jin, C. Xue, Q. Chen, G. Yang, K. Varga, Q. Xu,
Y. Li, Z. Liu, F. Liu, 2D PtS nanorectangles/g-C3N4 nanosheets with a metal
sulfide-support interaction effect for high-efficiency photocatalytic H2 evolution,
Mater. Horiz. 8 (2021), 612618.
[225] H. Dong, M. Xiao, S. Yu, H. Wu, Y. Wang, J. Sun, G. Chen, C. Li, Insight into the
activity and stability of RhxP nano-species supported on g-C3N4 for photocatalytic
H2 production, ACS Catal. 10 (1) (2020) 458–462.
[226] L. Bi, X. Liang, L. Zhang, J. Jiang, T. Hu, N. Wub, T. Xie, Boosting the
photogenerated charge separation of g-C3N4 by constructing a Ni@Ni2P
cocatalyst with a core-shell structure, New J. Chem. 46 (2022) 23379–23385.
[227] S. Chen, M. Li, S. Yang, X. Li, S. Zhang, Graphitied carbon-coated bimetallic FeCu
nanoparticles as original g-C3N4 cocatalysts for improving photocatalystic
activity, Appl. Surf. Sci. 492 (2019) 571–578.
[228] Z. Yan, Z. Sun, X. Liu, H. Jia, P. Du, Cadmium sulfide/graphitic carbon nitride
heterostructure nanowire loading with a nickel hydroxide cocatalyst for highly
efficient photocatalytic hydrogen production in water under visible light,
Nanoscale 8 (2016) 4748–4756.
[229] J. He, D. Zhang, X. Wang, J. Zhao, Y. Li, Y. Liu, F. Li, Phosphorylation of NiAl-
layered double hydroxide nanosheets as a novel cocatalyst for photocatalytic
hydrogen evolution, Int. J. Hydrogen Energy 46 (2021) 18977–18987.
[230] H. Zhao, Z. Jiang, K. Xiao, H. Sun, H. Chan, T. Tsang, S. Yang, P. Wong, Photo-
assisted separation of noble-metal-free oxidation and reduction cocatalysts for
graphitic carbon nitride nanosheets with efficient photocatalytic hydrogen
evolution, Appl. Catal. B 280 (2021), 119456.
[231] Z. Chen, K. Xia, X. She, Z. Mo, S. Zhao, J. Yi, Y. Xu, H. Chen, H. Xu, H. Li, 1D
metallic MoO2-C as co-catalyst on 2D g-C3N4 semiconductor to promote
photocatlaytic hydrogen production, Appl. Surf. Sci. 447 (2018) 732–739.
[232] Q. Zhu, B. Qiu, M. Du, M. Xing, J. Zhang, Nickel boride cocatalyst boosting
efficient photocatalytic hydrogen evolution reaction, Ind. Eng. Chem. Res. 57 (24)
(2018) 8125–8130.
[233] J. Chen, C.Y.Z. Guo, Y. Luo, C. Mao, Engineering ultrafine NiS cocatalysts as
active sites to boost photocatalytic hydrogen production of MgAl layered double
hydroxide, Appli. Surf. Sci 506 (2020), 144999.
[234] Y. Zhang, J. Shi, Z. Huang, X. Guan, S. Zong, C. Cheng, B. Zheng, L. Guo,
Synchronous construction of CoS2 in-situ loading and S doping for g-C3N4:
Enhanced photocatalytic H2-evolution activity and mechanism insight, Chem.
Eng. J. 401 (2020), 126135.
[235] D. Wei, Y. Liu, X. Shao, X. Zhao, S. Ghufran, L. Wang, R. Wu, J. Guo, C. Yang,
Cooperative effects of zinc-nickel sulfides as a dual cocatalyst for the enhanced
photocatalytic hydrogen evolution activity of g-C3N4, J. Environ. Chem. Eng. 10
(2) (2022), 107216.
[236] Y. Zou, J. Shi, D. Ma, Z. Fan, C. He, L. Cheng, D. Sun, J. Li, Z. Wang, C. Niu,
Efficient spatial charge separation and transfer in ultrathin g-C3N4 nanosheets
modified with Cu2MoS4 as a noble-metal-free co-catalyst for superior visible-light-
driven photocatalytic water splitting, Catal. Sci. Technol. 8 (2018) 3883–3893.
[237] K. Fang, Z. Chen, Y. Wei, S. Fang, Z. Dong, Y. Zhang, W. Li, L. Wang, Single site
Co-S anchored on carbon nitride as a highly active cocatalyst for photocatalytic
hydrogen evolution, J. Alloys Compd. 925 (2022), 166257.
52
Coordination Chemistry Reviews 500 (2024) 215489
[238] B. Wang, H. Cai, S. Shen, Single metal atom photocatalysis, Small Methods 3 (9)
(2019) 1800447.
[239] Z. Chen, E. Vorobyeva, S. Mitchell, E. Fako, M.A. Ortuño, N. López, S.M. Collins,
P.A. Midgley, S. Richard, G. Vilé, J. Pérez-Ramírez, A heterogeneous single-atom
palladium catalyst surpassing homogeneous systems for Suzuki coupling, Nat.
Nanotechnol. 13 (8) (2018) 702–707.
[240] X. Jiang, L. Zhang, H. Liu, D. Wu, F. Wu, L. Tian, L. Liu, J. Zou, S. Luo, B. Chen,
Silver single atom in carbon nitride catalyst for highly efficient photocatalytic
hydrogen evolution, Angew. Chem. Int. Ed. 59 (51) (2020) 23112–23116.
[241] K. Li, Y. Lin, K. Wang, Y. Wang, Y. Zhang, Y. Zhang, F. Liu, Rational design of
cocatalyst system for improving the photocatalytic hydrogen evolution activity of
graphite carbon nitride, Appl. Catal., B 268 (2020), 118402.
[242] A. Mehtab, S. Banerjee, Y. Mao, T. Ahmad, Type-II CuFe2O4/graphitic carbon
nitride heterojunctions for high-efficiency photocatalytic and electrocatalytic
hydrogen generation, ACS Appl. Mater. Interfaces 14 (39) (2022) 44317–44329.
[243] X. Zhao, Y. You, S. Huang, Y. Wu, Y. Ma, G. Zhang, Z. Zhang, Z-scheme
photocatalytic production of hydrogen peroxide over Bi4O5Br 2/g-C3N4
heterostructure under visible light, Appl. Catal., B 278 (2020), 119251.
[244] J. Wang, C. Liu, S. Yang, X. Lin, W. Shi, Fabrication of a ternary heterostructure
BiVO4 quantum dots/C60/g-C3N4 photocatalyst with enhanced photocatalytic
activity, J. Phys. Chem. Solids 136 (2020), 109164.
[245] M. Ismael, E. Elhaddad, M. Wark, Construction of SnO2/g-C3N4 composite
photocatalyst with enhanced interfacial charge separation and high efficiency for
hydrogen production and Rhodamine B degradation, Colloids Surf., A 638 (2022),
128288.
[246] Z. Liang, X. Meng, Y. Xue, X. Chen, Y. Zhou, X. Zhang, H. Cui, J. Tian, Facile
preparation of metallic 1T phase molybdenum selenide as cocatalyst coupled with
graphitic carbon nitride for enhanced photocatalytic H2 production, J. Colloid
Interface Sci. 598 (2021) 172–180.
[247] J. Xu, J. Gao, Y. Qi, C. Wang, L. Wang, Anchoring Ni2P on the UiO-66-NH2/g-
C3N4-derived C-doped ZrO2/g-C3N4 heterostructure: highly efficient
photocatalysts for H2 production from water splitting, ChemCatChem 10 (15)
(2018) 3327–3335.
[248] B. Zhang, H. Shi, Y. Yan, C. Liu, X. Hu, E. Liu, J. Fan, A novel S-scheme 1D/2D
Bi2S3/g-C3N4 heterojunctions with enhanced H2 evolution activity, Colloids Surf.,
A 608 (2021), 125598.
[249] J. Jia, W. Sun, Q. Zhang, X. Zhang, X. Hu, E. Liu, J. Fan, Recent advances in g-
C3N4-based heterojunction photocatalysts, J. Mater. Sci. Technol. 56 (2020) 1–17.
[250] X. Ruan, X. Cui, G. Jia, J. Wu, J. Zhao, D.J. Singh, Y. Liu, H. Zhang, L. Zhang,
W. Zheng, Intramolecular heterostructured carbon nitride with heptazine-triazine
for enhanced photocatalytic hydrogen evolution, Chem. Eng. J. 428 (2022),
132579.
[251] J. Xu, Z. Chen, J.A. Zapien, C. Lee, W. Zhang, Surface Engineering of ZnO
Nanostructures for Semiconductor-Sensitized Solar Cells, Adv. Mater. 26 (2014)
5337–5367.
[252] J. Chen, C. Dong, D. Zhao, Y. Huang, X. Wang, L. Samad, L. Dang, M. Shearer,
S. Shen, L. Guo, Molecular design of polymer heterojunctions for efficient solar-
hydrogen conversion, Adv. Mater. 29 (21) (2017) 1606198.
[253] J. Yan, P. Li, H. Bian, H. Wu, S. Liu, Synthesis of a nano-sized hybrid C3N4/TiO2
sample for enhanced and steady solar energy absorption and utilization,
Sustainable Energy & Fuels 1 (1) (2017) 95–102.
[254] D. Liu, S. Zhang, J. Wang, T. Peng, R. Li, Direct Z-Scheme 2D/2D photocatalyst
based on ultrathin g-C3N4 and WO3 nanosheets for efficient visible-light-driven
H2 generation, ACS Appl. Mat. Interfaces 11 (31) (2019) 27913–27923.
[255] S. Raheman AR, H.M. Wilson, B.M. Momin, U.S. Annapure, N. Jha, CdSe quantum
dots modified thiol functionalized g-C3N4: Intimate interfacial charge transfer
between 0D/2D nanostructure for visible light H2 evolution, Renewable Energy
158 (2020) 431–443.
[256] B. Lin, H. Li, H. An, W. Hao, J. Wei, Y. Dai, C. Ma, G. Yang, Preparation of 2D/2D
g-C3N4 nanosheet@ZnIn2S4 nanoleaf heterojunctions with well-designed high-
speed charge transfer nanochannels towards high-efficiency photocatalytic
hydrogen evolution, Appl. Catal., B 220 (2018) 542–552.
[257] M. Wang, S. Huang, X. Pang, M. Song, C. Du, Y. Su, Switching charge kinetics
from type-I to Z-scheme for g-C3N4 and ZnIn2S4 by defective engineering for
efficient and durable hydrogen evolution, Sustain. Energy. Fuels 3 (12) (2019)
3422–3429.
[258] H. Li, H. Yu, X. Quan, S. Chen, Y. Zhang, Uncovering the key role of the Fermi
level of the electron mediator in a Z-Scheme photocatalyst by detecting the charge
transfer process of WO3-metal-gC3N4 (Metal = Cu, Ag, Au), ACS Appl. Mat.
Interfaces 8 (3) (2016) 2111–2119.
[259] S. Wang, D. Li, C. Sun, S. Yang, Y. Guan, H. He, Synthesis and characterization of
g-C3N4/Ag3VO4 composites with significantly enhanced visible-light
photocatalytic activity for triphenylmethane dye degradation, Appl. Catal., B 144
(2014) 885–892.
[260] B. Zhu, W. Guo, J. Ran, H. Wang, J. Yu, S. Qiao, Metal-free 2D/2D phosphorene/
g-C3N4 Van der Waals heterojunction for highly enhanced visible-light
photocatalytic H2 production, Adv. Mater. 30 (25) (2018) e1800128.
[261] L. Liu, Y. Qi, J. Lu, S. Lin, W. An, Y. Liang, W. Cui, A stable Ag3PO4@g-C3N4
hybrid core@shell composite with enhanced visible light photocatalytic
degradation, Appl. Catal., B 183 (2016) 133–141.
[262] Y. Xu, L. Ding, Z. Wen, M. Zhang, D. Jiang, Y. Guo, C. Ding, K. Wang, Core-shell
LaFeO3@g-C3N4 p-n heterostructure with improved photoelectrochemical
performance for fabricating streptomycin aptasensor, Appl. Surf. Sci. 511 (2020),
145571.
D. Ma et al.
[263] D. Gao, W. Liu, Y. Xu, P. Wang, J. Fan, H. Yu, Core-shell Ag@Ni cocatalyst on the
TiO2 photocatalyst: One-step photoinduced deposition and its improved H2-
evolution activity, Appl. Catal., B 260 (2020), 118190.
[264] J. Pan, Z. Dong, B. Wang, Z. Jiang, C. Zhao, J. Wang, C. Song, Y. Zheng, C. Li, The
enhancement of photocatalytic hydrogen production via Ti3+ self-doping black
TiO2/g-C3N4 hollow core-shell nano-heterojunction, Appli. Catal. B 242 (2018)
92–99.
[265] J. Kang, S. Byun, S. Kim, J. Lee, M. Jung, H. Hwang, T.W. Kim, S.H. Song, D. Lee,
Design of three-dimensional hollow-sphere architecture of Ti3C2TxMXene with
graphitic carbon nitride nanoshells for efficient photocatalytic hydrogen
evolution, ACS Appl. Energy Mater. 3 (9) (2020) 9226–9233.
[266] S. Liang, G. Sui, D. Guo, Z. Luo, R. Xu, H. Yao, J. Li, C. Wang, g-C3N4-wrapped
nickel doped zinc oxide/carbon core-double shell microspheres for high-
performance photocatalytic hydrogen production, J. Colloid Interface Sci. 635
(2023) 83–93.
[267] F. Guo, X. Huang, Z. Chen, Y. Shi, H. Sun, X. Cheng, W. Shi, L. Chen, Formation of
unique hollow ZnSnO3@ZnIn2S4 core-shell heterojunction to boost visible-light-
driven photocatalytic water splitting for hydrogen production, J. Colloid Interface
Sci. 602 (2021) 889–897.
[268] F. Shaik, R. Milan, L. Amirav, Gold@Carbon Nitride Yolk and Core-Shell
Nanohybrids, ACS Appli. Mater. Interfaces 14 (18) (2022) 21340–21347.
[269] A. Cao, L. Zhang, Y. Wang, H. Zhao, X. Liu, Z. Lin, X. Su, F. Yue, 2D–2D
Heterostructured UNiMOF/g-C3N4 for Enhanced Photocatalytic H2 Production
under Visible-Light Irradiation, ACS Sustainable Chem. Eng. 7 (2) (2019)
2492–2499.
[270] H. Xu, X. She, T. Fei, Y. Song, D. Liu, H. Li, X. Yang, J. Yang, H. Li, L. Song, P.
M. Ajayan, J. Wu, Metal-oxide-mediated subtractive manufacturing of two-
dimensional carbon nitride for high-efficiency and high-yield photocatalytic H2
evolution, ACS Nano 13 (10) (2019) 11294–11302.
[271] H. Zhu, X. Yang, M. Zhang, Q. Li, J. Yang, Construction of 2D/2D TiO2/g-C3N4
nanosheet heterostructures with improved photocatalytic activity, Mater. Res.
Bull. 125 (2020), 110765.
[272] B. Song, Z. Zeng, G. Zeng, J. Gong, R. Xiao, S. Ye, M. Chen, C. Lai, P. Xu, X. Tang,
Powerful combination of g-C3N4 and LDHs for enhanced photocatalytic
performance: A review of strategy, synthesis, and applications, Adv. Colloid
Interface Sci. 272 (2019), 101999.
[273] L. Jiang, X. Yuan, G. Zeng, Z. Wu, J. Liang, X. Chen, L. Leng, H. Wang, H. Wang,
Metal-free efficient photocatalyst for stable visible-light photocatalytic
degradation of refractory pollutant, Appl. Catal., B 221 (2018) 715–725.
[274] Y. Zou, J. Shi, D. Ma, Z. Fan, L. Lu, C. Niu, In situ synthesis of C-doped TiO2@g-
C3N4 core-shell hollow nanospheres with enhanced visible-light photocatalytic
activity for H2 evolution, Chem. Eng. J. 322 (2017) 435–444.
[275] J. Liu, Origin of high photocatalytic efficiency in monolayer g-C3N4/CdS
heterostructure: A hybrid DFT study, J. Phys. Chem. C 119 (2015) 28417–28423.
[276] G. Fang, M. Li, H. Shen, S. Yang, J. Israrc, Enhanced photocatalytic characteristics
and low selectivity of a novel Z-scheme TiO2/g-C3N4/Bi2WO6 heterojunction
under visible light, Mater. Sci. Semicond. Process. 121 (2021), 105374.
[277] Q. Wang, W. Wang, L. Zhong, D. Liu, X. Cao, F. Cui, Oxygen vacancy-rich 2D/2D
BiOCl-g-C3N4 ultrathin heterostructure nanosheets for enhanced visible-light-
driven photocatalytic activity in environmental remediation, Appl. Catal., B 220
(2018) 290–302.
[278] S. Yin, J. Di, M. Li, Y. Sun, J. Xia, H. Xu, W. Fan, H. Li, Ionic liquid-assisted
synthesis and improved photocatalytic activity of p-n junction g-C3N4/BiOCl,
J. Mater. Sci. 51 (2016) 4769–4777.
[279] Y. Xia, Y. He, X. Liu, R. Huang, R. Liang, F. Chen, G. Yan, Selective deposition of
cocatalyst NiS on a g-C3N4/ZnIn2S4 heterojunction for exceptional photocatalytic
H2 evolution, New J. Chem. 46 (2022) 14502–14509.
[280] Y. Xu, Y. E, G. Wang, Controlled growth of “cookie-like” ZnIn2S4 nanoparticles on
g-C3N4 for enhanced visible light photocatalytic activity, Inorg. Chem. Commun.
108 (2019), 107485.
[281] K. Ikeue, Y. Yamamoto, M. Suzuki, Photocatalytic activity for hydrogen evolution
of heteroatom-doped SrTiO3 prepared using a graphitic-carbon nitride nanosheet,
Ceramics 3 (1) (2020) 22–30.
[282] Y. Luo, B. Deng, Y. Pu, A. Liu, J. Wang, K. Ma, F. Gao, B. Gao, W. Zou, L. Dong,
Interfacial coupling effects in g-C3N4/SrTiO3 nanocomposites with enhanced H2
evolution under visible light irradiation, Appl. Catal., B 247 (2019) 1–9.
[283] M. Tan, Y. Ma, C. Yu, Q. Luan, J. Li, C. Liu, W. Dong, Y. Su, L. Qiao, L. Gao, Q. Lu,
Y. Bai, Boosting photocatalytic hydrogen production via interfacial engineering
on 2D ultrathin Z-scheme ZnIn2S4/g-C3N4 heterojunction, Adv. Funct. Mater. 32
(14) (2022) 2111740.
[284] T. Hong, S. Anwer, J. Wu, C. Deng, H. Qian, Semiconductor-metal- semiconductor
TiO2@Au/g-C3N4 interfacial heterojunction for high performance Z-scheme
photocatalyst, Front. Chem. 1050046 (2022).
[285] W. Ge, K. Liu, S. Deng, P. Yang, L. Shen, Z-scheme g-C3N4/ZnO heterojunction
decorated by Au nanoparticles for enhanced photocatalytic hydrogen production,
Appl. Surf. Sci. 607 (2023), 155036.
[286] S. Li, M. Zhang, Z. Qu, X. Cui, Z. Liu, C. Piao, S. Li, J. Wang, Y. Song, Fabrication
of highly active Z-scheme Ag/g-C3N4-Ag-Ag3PO4 (110) photocatalyst for visible
light photocatalytic degradation of levofloxacin with simultaneous hydrogen
production, Chem. Eng. J. 382 (2020), 122394.
[287] L. Qian, Y. Hou, Z. Yu, M. Li, F. Li, L. Sun, W. Luo, G. Pan, Metal-induced Z-
scheme CdS/Ag/g-C3N4 photocatalyst for enhanced hydrogen evolution under
visible light: The synergy of MIP effect and electron mediator of Ag, Mol. Catal.
458 (2018) 43–51.
[288] S. Patnaik, G. Swain, K.M. Parida, Highly efficient charge transfer through a
double Z-scheme mechanism by a Cu-promoted MoO3/g-C3N4 hybrid
53
Coordination Chemistry Reviews 500 (2024) 215489
nanocomposite with superior electrochemical and photocatalytic performance,
Nanoscale 10 (2018) 5950–5964.
[289] Y. Zou, J. Shi, D. Ma, Z. Fan, C. Niu, L. Wang, Fabrication of g-C3N4/Au/C-TiO2
hollow structures as visible-light-driven z-scheme photocatalysts with enhanced
photocatalytic H2 evolution, ChemCatChem 9 (2017) 3752–3761.
[290] L. Tian, X. Yang, X. Cui, Q. Liu, H. Tang, Fabrication of dual direct Z-scheme g-
C3N4/MoS2/Ag3PO4 photocatalyst and its oxygen evolution performance, Appl.
Surf. Sci. 463 (2019) 9–17.
[291] Y.O. Ibrahim, A. Hezam, T.F. Qahtan, A.H. Al-Aswad, M.A. Gondal, Q.A. Drmosh,
Laser-assisted synthesis of Z-scheme TiO2/rGO/g-C3N4 nanocomposites for highly
enhanced photocatalytic hydrogen evolution, Appl. Surf. Sci. 534 (2020),
147578.
[292] F. Chen, L. Cheng, Y. Tang, K. Shu, W. Shi, Construction of Z-scheme
heterojunction g-C3N4/CQDs/InVO4 with broad-spectrum response for efficient
rhodamine B degradation and H2 evolution under visible light, J. Chem. Technol.
Biotechnol. 96 (11) (2021) 3074–3083.
[293] K. Zhu, C. Wang, X. Luan, J. Li, P. Yang, Efficient charge transfer in Z-scheme g-
C3N4/Cu/MoS2 heterojunctions for enhanced photocatalysis and photoenhanced
electrocatalysis, Adv. Mater. 9 (2022) 2201114.
[294] S. Feng, T. Chen, Z. Liu, J. Shi, X. Yue, Y. Li, Z-scheme CdS/CQDs/g-C3N4
composites with visible-near-infrared light response for efficient photocatalytic
organic pollutant degradation, Sci. Total Environ. 704 (2020), 135404.
[295] Y. Wu, M. Song, Z. Chai, J. Huang, X. Wang, Facile construction of Bi2MoO6/Bi/g-
C3N4 toward efficient photocatalytic oxidation of indoor gaseous formaldehyde
with a wide concentration range under visible light irradiation, ACS Sustain.
Chem. Eng. 8 (20) (2020) 7710–7720.
[296] W. Jo, N.C.S. Selvam, Z-scheme CdS/g-C3N4 composites with RGO as an electron
mediator for efficient photocatalytic H2 production and pollutant degradation,
Chem. Eng. J. 317 (2017) 913–924.
[297] Z. Zhu, P. Huo, Z. Lu, Y. Yan, Z. Liu, W. Shi, C. Li, H. Dong, Fabrication of
magnetically recoverable photocatalysts using g-C3N4 for effective separation of
charge carriers through like-Z-scheme mechanism with Fe3O4 mediator, Chem.
Eng. J. 331 (2018) 615–625.
[298] Q. Xu, L. Zhang, B. Cheng, J. Fan, J. Yu, S-scheme heterojunction photocatalyst,
Chem. 6 (7) (2020) 1543–1559.
[299] Z. Pan, G. Zhang, X. Wang, Polymeric carbon nitride/reduced graphene oxide/
Fe2O3: all-solid-state Z-scheme system for photocatalytic overall water splitting,
Angew. Chem. Int. Ed. 58 (21) (2019) 7102–7106.
[300] X. Li, B. Kang, F. Dong, Z. Zhang, X. Luo, L. Han, J. Huang, Z. Feng, Z. Chen, J. Xu,
B. Peng, Z.L. Wang, Enhanced photocatalytic degradation and H2/H2O2
production performance of S-pCN/WO2.72 S-scheme heterojunction with
appropriate surface oxygen vacancies, Nano Energy 81 (2021), 105671.
[301] F. Dong, Z. Zhao, T. Xiong, Z. Ni, W. Zhang, Y. Sun, W. Ho, In situ construction of
g-C3N4/g-C3N4 metal-free heterojunction for enhanced visible-light
photocatalysis, ACS Appl. Mater. Interfaces 5 (2013) 11392–11401.
[302] Y. Chen, F. Su, H. Xie, R. Wang, C. Ding, J. Huang, Y. Xu, L. Ye, One-step
construction of S-scheme heterojunctions of N-doped MoS2 and S doped g-C3N4
for enhanced photocatalytic hydrogen evolution, Chem. Eng. J. 404 (2021),
126498.
[303] T. Yan, H. Liu, Z. Jin, g-C3N4/α-Fe2O3 supported zero-dimensional Co3S4
nanoparticles form S–scheme heterojunction photocatalyst for efficient hydrogen
production, Energy Fuels 35 (2021) 856–867.
[304] B. Zhang, X. Hu, E. Liu, J. Fan, Novel S-scheme 2D/2D BiOBr/g-C3N4
heterojunctions with enhanced photocatalytic activity, Chin. J. Catal. 42 (2021)
1519–1529.
[305] J. Fu, Q. Xu, J. Low, C. Jiang, J. Yu, Ultrathin 2D/2D WO3/g-C3N4 step-scheme
H2-production photocatalyst, Appl. Catal., B 243 (2019) 556–565.
[306] J. Jiang, Z. Xiong, H. Wang, G. Liao, S. Bai, J. Zou, P. Wu, P. Zhang, X. Li, Sulfur-
doped g-C3N4/g-C3N4 isotype step-scheme heterojunction for photocatalytic H2
evolution, J. Mater. Sci. Technol. 118 (2022) 15–24.
[307] Q. Li, W. Zhao, Z. Zhai, K. Ren, T. Wang, H. Guan, H. Shi, 2D/2D Bi2MoO6/g-C3N4
S-scheme heterojunction photocatalyst with enhanced visible-light activity by Au
loading, J. Mater. Sci. Technol. 56 (2020) 216–226.
[308] D. Ren, W. Zhang, Y. Ding, R. Shen, Z. Jiang, X. Lu, X. Li, In situ fabrication of
robust cocatalyst-free CdS/g-C3N42D-2D step-scheme heterojunctions for highly
active H2 evolution, Sol. RRL 4 (2020) 1900423.
[309] G. Gogoi, S. Keene, A.S. Patra, T.K. Sahu, S. Ardo, M. Qureshi, Hybrid of g-C3N4
and MoS2 integrated onto Cd0.5Zn0.5S: Rational design with efficient charge
transfer for enhanced photocatalytic activity, ACS Sustain, Chem. Eng. 6 (5)
(2018) 6718–6729.
[310] S. Obregón, Y.F. Zhang, G. Colón, Cascade charge separation mechanism by
ternary heterostructured BiPO4/TiO2/g-C3N4 photocatalyst, Appl. Catal., B 184
(2016) 96–103.
[311] Z. Dong, Y. Wu, N. Thirugnanam, G. Li, Double Z-scheme ZnO/ZnS/ g-C3N4
ternary structure for efficient photocatalytic H2 production, Appl. Surf. Sci. 430
(2018) 293–300.
[312] Q. Li, L. Xu, K. Luo, W. Huang, L. Wang, X. Li, G. Huang, Y. Yu, Insights into
enhanced visible-light photocatalytic activity of C60 modified g-C3N4 hybrids: the
role of nitrogen, Phys. Chem. Chem. Phys. 18 (2016) 33094–33102.
[313] B. Chai, X. Liao, F. Song, H. Zhou, Fullerene modified C3N4 composites with
enhanced photocatalytic activity under visible light irradiation, Dalton Trans. 43
(2014) 982–989.
[314] W. Shi, J. Wang, S. Yang, X. Lin, F. Guo, J. Shi, Fabrication of a ternary carbon
dots/CoO/g-C3N4 nanocomposite photocatalyst with enhanced visible-light-
driven photocatalytic hydrogen production, J. Chem. Technol. Biotechnol. 95
(2020) 2129–2138.
D. Ma et al.
[315] Y. Li, X. Feng, Z. Lu, H. Yin, F. Liu, Q. Xiang, Enhanced photocatalytic H2-
production activity of C-dots modified g-C3N4/TiO2 nanosheets composites,
J. Colloid Interface Sci. 513 (2018) 866–876.
[316] J. Liu, H. Xu, Y. Xu, Y. Song, J. Lian, Y. Zhao, L. Wang, L. Huang, H. Ji, H. Li,
Graphene quantum dots modified mesoporous graphite carbon nitride with
significant enhancement of photocatalytic activity, Appl. Catal., B 207 (2017)
429–437.
[317] T. Ishaq, M. Yousaf, I.A. Bhatti, M. Ahmad, M. Ikram, M.U. Khan, A. Qayyum,
Photo-assisted splitting of water into hydrogen using visible-light activated silver
doped g-C3N4 & CNTs hybrids, Int. J. Hydrogen Energy 45 (56) (2020)
31574–31584.
[318] L. Song, X. Kang, S. Zhang, CNT/g-C3N4 photocatalysts with enhanced hydrogen
evolution ability for water splitting based on a noncovalent interaction, Int. J.
Energy Res. 42 (2018) 1649–1656.
[319] J. Sun, Y. Huang, H. Li, Y. Qiu, J. Zhang, K. Hu, J. Li, Y. Ding, Silver nanoparticle-
loaded graphitic carbon nitride/multiwall carbon nanotube composite with
improved denitrification to nitrogen gas for the photocatalytic removal of
aqueous ammonia nitrogen, Environ. Technol. Innov. 24 (2021), 101815.
[320] Q. Xu, B. Cheng, J. Yu, G. Liu, Making co-condensed amorphous carbon/g-C3N4
composites with improved visible-light photocatalytic H2-production
performance using Pt as cocatalyst, Carbon 118 (2017) 241–249.
[321] Y. Li, H. Xu, S. Ouyang, J. Ye, Metal-organic frameworks for photocatalysis, Phys.
Chem. Chem. Phys. 18 (11) (2016) 7563–7572.
[322] S.A. Younis, E.E. Kwon, M. Qasim, K.H. Kim, T. Kim, D. Kukkar, X. Dou, I. Ali,
Metal-organic framework as a photocatalyst: progress in modulation strategies
and environmental/energy applications, Prog. Energy Combust. Sci. 81 (2020),
100870.
[323] T. Chen, L. Wang, Y. Wang, H. Gao, J. He, G. Wang, X. Meng, Y. Wu, Y. Deng,
C. Wan, Facile Strategy for Efficient Charge Separation and High Photoactivity of
Mixed-Linker MOFs, ACS Appl. Mater. Interfaces 13 (17) (2021) 20897–20905.
[324] J. Ran, J. Qu, H. Zhang, T. Wen, H. Wang, S. Chen, L. Song, X. Zhang, L. Jing,
R. Zheng, S. Qiao, 2D metal organic framework nanosheet: a universal platform
promoting highly efficient visible-light-induced hydrogen production, Adv.
Energy Mater. (2019) 9 1803402.
[325] L. Lu, B. Wu, W. Shi, P. Cheng, Metal-organic framework-derived heterojunctions
as nanocatalysts for photocatalytic hydrogen production, Inorg. Chem. Front. 6
(12) (2019) 3456–3467.
[326] Y. Liu, Z. Xiang, Fully conjugated covalent organic polymer with carbon
encapsulated Ni2P for highly sustained photocatalytic H2 production from
seawater, ACS Appl. Mater. Interfaces, Am. Chem. Soc. 11 (2019) 41313–41320.
[327] M. Zhang, Q. Shang, Y. Wan, Q. Cheng, G. Liao, Z. Pan, Self-template synthesis of
double-shell TiO2@ZIF-8 hollow nanospheres via sonocrystallization with
enhanced photocatalytic activities in hydrogen generation, Appl. Catal. B 241
(2019) 149–158.
[328] Z. Yu, L. Qian, T. Zhong, Q. Ran, J. Huang, Y. Hou, F. Li, M. Li, Q. Sun, H. Zhang,
Enhanced visible light photocatalytic activity of CdS through controllable self-
assembly compositing with ZIF-67, Mol. Catal. 485 (2020), 110797.
[329] R. Wang, L. Gu, J. Zhou, X. Liu, F. Teng, C. Li, Y. Shen, Y. Yuan, Quasi-polymeric
metal-organic framework UiO-66/g-C3N4 heterojunctions for enhanced
photocatalytic hydrogen evolution under visible light irradiation, Adv. Mater.
Interfaces 2 (2015) 1500037.
[330] J. Pu, Z. Jin, Y. Cheng, W. Yuan, g-C3N4/Cu3P/UiO-66 ternary composites for
enhanced visible light photocatalytic H2 evolution, ChemistrySelect 4 (2019)
5459–5469.
[331] S. Zhao, J. Xu, M. Mao, L. Li, X. Li, Protonated g-C3N4 cooperated with Co-MOF
doped with Sm to construct 2D/2D heterojunction for integrated dye-sensitized
photocatalytic H2 evolution, J. Colloid Interface Sci. 583 (2021) 435–447.
[332] Z. Pu, B. Xiao, S. Mao, Y. Sun, D. Ma, H. Wang, J. Zhou, Y. Cheng, J. Shi, An
electron-hole separation mechanism caused by the pseudo-gap formed at the
interfacial Co-N bond between cobalt porphyrin metal organic framework and
boron-doped g-C3N4 for boosting photocatalytic H2 production, J. Colloid
Interface Sci. 628 (2022) 477–487.
[333] D. Ma, J. Shi, Z. Pu, S. Mao, X. Xu, D. He, R. Guo, F. Chen, Decorating phosphorus-
doped g-C3N4 with zinc porphyrin metal-organic framework via an electrostatic
self-assembly process: An efficient strategy to boost photocatalytic hydrogen
evolution performance, Sol. RRL 6 (2022) 2200714.
[334] N. Arif, Y. Lin, K. Wang, Y. Dou, Y. Zhang, K. Li, S. Liu, F. Liu, Bimetallic zeolite-
imidazole framework-based heterostructure with enhanced photocatalytic
hydrogen production activity, RSC Adv. 11 (2021) 9048–9056.
[335] A. Rajan, B. Neppolian, Coordinative integration of amorphous nickel-imidazole
framework with graphitic carbon nitride for enhanced photocatalytic hydrogen
production, Appl. Mater. Today 28 (2022), 101524.
[336] Y. Zhang, Z. Jin, A. luan, G. Wang, Charge transfer behaviors over MOF-5@g-
C3N4 with NixMo1-xS2 modification, Int. J. Hydrogen Energy 43 (2018)
9914–9923.
[337] X. Li, J.G. Yu, M. Jaroniec, Hierarchical photocatalysts, Chem. Soc. Rev. 45
(2016) 2603–2636.
[338] H. Li, Y. Zhou, W. Tu, J. Ye, Z. Zou, State-of-the-art progress in diverse
heterostructured photocatalysts toward promoting photocatalytic performance,
Adv. Funct. Mater. 25 (2015) 998–1013.
[339] G. Liu, G. Zhao, W. Zhou, Y. Liu, H. Pang, H. Zhang, D. Hao, X. Meng, P. Li,
T. Kako, J. Ye, In situ bond modulation of graphitic carbon nitride to construct p-n
homojunctions for enhanced photocatalytic hydrogen production, Adv. Funct.
Mater. 26 (2016) 6822–6829.
54
Coordination Chemistry Reviews 500 (2024) 215489
[340] Z. Zeng, H. Yu, X. Quan, S. Chen, S. Zhang, Structuring phase junction between
tris -triazine and triazine crystalline C3N4 for efficient photocatalytic hydrogen
evolution, Appl. Catal., B 227 (2018) 153–160.
[341] Y.W. Liao, G.H. Wang, J. Wang, K. Wang, S.D. Yan, Y.R. Su, Nitrogen vacancy
induced in situ g-C3N4 p-n homojunction for boosting visible light-driven
hydrogen evolution, J. Colloid Interf. Sci. 587 (2021) 110–120.
[342] Y. Zheng, Y. Liu, X. Guo, W. Zhang, Y. Wang, M. Zhang, R. Li, Z. Peng, H. Xie,
Y. Huang, In-situ construction of morphology-controllable OD/1D g-C3N4
homojunction with enhanced photocatalytic activity, Appl. Surf. Sci. 563 (2021),
150317.
[343] P. Ma, X. Zhang, C. Wang, Z. Wang, K. Wang, Y. Feng, J. Wang, Y. Zhai, J. Deng,
L. Wang, K. Zheng, Band alignment of homojunction by anchoring CN quantum
dots on g-C3N4 (0D/2D) enhance photocatalytic hydrogen peroxide evolution,
Appl. Catal., B 300 (2022), 120736.
[344] Y. Lv, D. Ma, K. Song, S. Mao, Z. Liu, D. He, X. Zhao, T. Yao, J. Shi, Graphitic
carbon nitride decorated with C-N compounds broken by s-triazine unit as
homojunction for photocatalytic H2 evolution, J. Mater. Chem. A 11 (2023)
800–808.
[345] H. Sun, Y. Shi, W. Shi, F. Guo, High-crystalline/amorphous g-C3N4 S-scheme
homojunction for boosted photocatalytic H2 production in water/simulated
seawater: Interfacial charge transfer and mechanism insight, Appl. Surf. Sci. 593
(2022), 153281.
[346] J. Li, X. Liu, H. Che, C. Liu, C. Li, Facile construction of O-doped crystalline/non-
crystalline g-C3N4 embedded nano-homojunction for effificiently photocatalytic
H2 evolution, Carbon 172 (2021) 602–612.
[347] Z. Liu, G. Wang, H.S. Chen, P. Yang, An amorphous/crystalline g-C3N4
homojunction for visible light photocatalysis reactions with superior activity,
Chem. Commun. 54 (2018) 4720–4723.
[348] J. Li, X. Liu, H. Che, C. Liu, C. Li, Facile construction of O-doped crystalline/non-
crystalline g-C3N4 embedded nano-homojunction for efficiently photocatalytic H2
evolution, Carbon 172 (2021) 602–612.
[349] C. Li, T. Song, C. Xie, W. Shi, Dan Wang, P. Yang, Two-step polymerization
nanoarchitectonics for superior thin g-C3N4 nanosheets with modulated band gap
and enhanced photo- and electrochemical performance, Inter. J. Hydrogen
Energy 48 (2023) 2677–2688.
[350] Y. Zheng, Y. Liu, X. Guo, W. Zhang, Y. Wang, M. Zhang, R. Li, Z. Peng, H. Xie,
Y. Huang, In-situ construction of morphology-controllable 0D/1D g-C3N4
homojunction with enhanced photocatalytic activity, Appl. Surf. Sci. 563 (2021),
150317.
[351] R. Tang, Y. Zhou, S. Xiong, Y. Deng, L. Li, Z. Zhou, H. Zeng, J. Wang, J. Zhao,
D. Gong, Multiscale modification of carbon nitride-based homojunction for
enhanced photocatalytic atrazine decomposition, J. Colloid Interf. Sci. 630 (2023)
127–139.
[352] C. Feng, X. Ouyang, Y. Deng, J. Wang, L. Tang, A novel g-C3N4/g-C3N4-x
homojunction with efficient interfacial charge transfer for photocatalytic
degradation of atrazine and tetracycline, J. Hazard. Mater. 441 (2023), 129845.
[353] L.X. Nong, V.H. Nguyen, T. Lee, T.D. Nguyen, Fabrication of g-C3N4 with
simultaneous isotype heterojunction and porous structure for enhanced
visible–light–driven photocatalytic performance toward tetracycline
hydrochloride elimination, Top. Catal. 66 (2023) 275–288.
[354] S. Tan, Z. Xing, J. Zhang, Z. Li, X. Wu, J. Cui, J. Kuang, J. Yin, W. Zhou, Meso-g-
C3N4/g-C3N4 nanosheets laminated homojunctions as efficient visible-light-driven
photocatalysts, Int. J. Hydrogen Energy 42 (2017) 25969–25979.
[355] W. Xing, Y. Zhang, J. Zou, T. Zhang, C. Liu, G. Wu, G. Chen, Sulfur-doped 2D/3D
carbon nitride-based van der Waals homojunction with superior photocatalytic
hydrogen evolution and wastewater purification, Int. J. Hydrogen Energy 47
(2022) 12559–12568.
[356] M. Ren, X. Zhang, Y. Liu, G. Yang, L. Qin, J. Meng, Y. Guo, Y. Yang, Interlayer
palladium-single-atom-coordinated cyano-group-rich graphitic carbon nitride for
enhanced photocatalytic hydrogen production performance, ACS Catal. 12 (2022)
5077–5093.
[357] G. Liu, H. Lv, Y. Zeng, M. Yuan, Q. Meng, Y. Wang, C. Wang, Single–atom Pd-N3
sites on carbon–defcient g-C3N4 for photocatalytic H2 evolution, Trans. Tianjin
Uni. 27 (2021) 139–146.
[358] X. Li, W. Bi, L. Zhang, S. Tao, W. Chu, Q. Zhang, Y. Luo, C. Wu, Y. Xie, Single-atom
Pt as co-catalyst for enhanced photocatalytic H2 evolution, Adv. Mater. 28 (2016)
2427–2431.
[359] C. Wang, K. Wang, Y. Feng, C. Li, X. Zhou, L. Gan, Y. Feng, H. Zhou, B. Zhang,
X. Qu, H. Li, J. Li, A. Li, Y. Sun, S. Zhang, G. Yang, Y. Guo, S. Yang, T. Zhou,
F. Dong, K. Zheng, L. Wang, J. Huang, Z. Zhang, X. Han, Co and Pt dual-single-
atoms with oxygen-coordinated Co-O-Pt dimer sites for ultrahigh photocatalytic
hydrogen evolution efficiency, Adv. Mater. 33 (2021) 2003327.
[360] J. Cai, A. Cao, Z. Wang, S. Lu, Z. Jiang, X.-Y. Dong, X. Li, S.-Q. Zang, Surface
oxygen vacancies promoted Pt redispersion to single-atoms for enhanced
photocatalytic hydrogen evolution, J. Mater. Chem. A 9 (2021) 13890–13897.
[361] W. Xi, K. Wang, Y. Shen, M. Ge, Z. Deng, Y. Zhao, Q. Cao, Y. Ding, G. Hu, J. Luo,
Dynamic co-catalysis of Au single atoms and nanoporous Au for methane
pyrolysis, Nat. Commun. 2020 (1919) 11.
[362] C. Yang, Z. Cheng, G. Divitini, C. Qian, B. Hou, Y. Liao, A Ni or Co single atom
anchored conjugated microporous polymer for high-performance photocatalytic
hydrogen evolution, J. Mater. Chem. A 9 (2021) 19894–19900.
[363] X. Xiao, Y. Gao, L. Zhang, J. Zhang, Q. Zhang, Q. Li, H. Bao, J. Zhou, S. Miao,
N. Chen, J. Wang, B. Jiang, C. Tian, H. Fu, A promoted charge separation/transfer
system from Cu single atoms and C3N4 layers for efficient photocatalysis, Adv.
Mater. 32 (2020) e2003082.
D. Ma et al.
[364] C. Li, X. Dong, Y. Zhang, J. Hu, J. Yuan, G. Li, D. Chen, Y. Li, Micro-tailored g-
C3N4 enables Ru single-atom loading for efficient photocatalytic H2 evolution,
Appl. Surf. Sci. 596 (2022), 153471.
[365] M.V. Jyothirmai, D. Roshini, B. Moses Abraham, J.K. Singh, Accelerating the
Discovery of g-C3N4-supported single atom catalysts for hydrogen evolution
reaction: a combined dft and machine learning strategy, ACS Appl. Energy Mater.
6 (2023) 5598–5606.
[366] X. Jiang, L. Zhang, H. Liu, D. Wu, F. Wu, L. Tian, L. Liu, J. Zou, S. Luo, B. Chen,
Silver single atom in carbon nitride catalyst for highly efficient photocatalytic
hydrogen evolution, Angew. Chem. Int. Ed. 59 (2020) 23112–23116.
[367] F. Wang, Y. Wang, Y. Feng, Y. Zeng, Z. Xie, Q. Zhang, Y. Su, P. Chen, Y. Liuc,
K. Yao, W. Lv, G. Liu, Novel ternary photocatalyst of single atom-dispersed silver
and carbon quantum dots co-loaded with ultrathin g-C3N4 for broad spectrum
photocatalytic degradation of naproxen, Appl. Catal., B. 221 (2018) 510–520.
[368] Y. Zhu, T. Wang, T. Xu, Y. Li, C. Wang, Size effect of Pt co-catalyst on
photocatalytic efficiency of g-C3N4 for hydrogen evolution, Appl. Surf. Sci. 464
(2019) 36–42.
[369] L. Zhang, Q. Luo, S. Hu, Z. Hu, W. Zhang, J. Yang, Enhanced electron-hole
separation in phosphorus-coordinated Co atom on g-C3N4 toward photocatalytic
overall water splitting, J. Phys. Chem. Lett. 13 (2022) 11961–11967.
[370] Y. Huang, Y. Li, K.T. Arul, T. Ohigashi, T.T.T. Nga, Y. Lu, C. Chen, J. Chen,
S. Shen, W. Pong, C. Dong, W. Chou, Atomic nickel on graphitic carbon nitride as
a visible light-driven hydrogen production photocatalyst studied by X–ray
spectromicroscopy, ACS Sustain. Chem. Eng. 11 (2023) 5390–5399.
[371] C. Yang, Z. Zhao, Q. Liu, Regulating effect on photocatalytic water splitting
performance of g-C3N4 via confinement of single atom Pt based on energy band
engineering: A first principles investigation, Appl. Surf. Sci. 577 (2022), 151916.
[372] R. Xu, B. Xu, X. You, D. Shao, G. Gao, F. Li, X. Wang, Y. Yao, Preparation of single-
atom palladium catalysts with high photocatalytic hydrogen production
performance by means of photochemical reactions conducted with frozen
precursor solutions, J. Mater. Chem. A 11 (2023) 11202.
[373] H. Zhai, P. Tan, M. Jiang, M. Zhang, R. Ren, R. Sa, J. Pan, Electronic regulation of
Pt single-atom catalysts via local coordination state adjustment for enhanced
photocatalytic performance, ACS Catal. 13 (2023) 8063–8072.
[374] S. Li, X. Lu, S. Zhao, M. Ceccato, X. Hu, A. Roldan, M. Liu, K. Daasbjerg, p-Block
indium single-atom catalyst with low-coordinated In-N motif for enhanced
electrochemical CO2 reduction, ACS Catal. 12 (2022) 7386–7395.
[375] F. Meng, Z. Tian, W. Tian, H. Zhang, Advances in carbon nitride supported single-
atom photocatalysts for hydrogen evolution, Curr. Opin. Chem. Eng. 41 (2023),
100941.
55
Coordination Chemistry Reviews 500 (2024) 215489
[376] Q. Wang, K. Liu, J. Fu, C. Cai, H. Li, Y. Long, S. Chen, B. Liu, H. Li, W. Li, X. Qiu,
N. Zhang, J. Hu, H. Pan, M. Liu, Atomically dispersed s-block magnesium sites for
electroreduction of CO2 to CO, Angew. Chem. Int. Ed. 60 (2021) 25241–25245.
[377] K. Fang, Z. Chen, Y. Wei, S. Fang, Z. Dong, Y. Zhang, Single site Co-S anchored on
carbon nitride as a highly active cocatalyst for photocatalytic hydrogen evolution,
J. Alloy. Compound. 925 (2022), 166257.
[378] Y. Xiao, S. Guo, G. Tian, B. Jiang, Z. Ren, C. Tian, W. Li, H. Fu, Synergetic
enhancement of surface reactions and charge separation over holey C3N4/TiO2 2D
heterojunctions, Sci. Bull. 66 (3) (2021) 275–283.
[379] Y. Qin, H. Li, J. Lu, Y. Feng, F. Meng, C. Ma, Y. Yan, M. Meng, Synergy between
van der waals heterojunction and vacancy in ZnIn2S4/g-C3N4 2D/2D
photocatalysts for enhanced photo catalytic hydrogen evolution, Appl. Catal., B
277 (2020), 119254.
[380] J. Zhang, Q. Zhu, L. Wang, M. Nasir, S. Cho, J. Zhang, g-C3N4/CoAl-LDH 2D/2D
hybrid heterojunction for boosting photocatalytic hydrogen evolution, Int. J.
Hydrogen Energy 45 (41) (2020) 21331–21340.
[381] Q. Song, S. Heng, W. Wang, H. Guo, H. Li, D. Dang, Binary type-II heterojunction
K7HNb6O19/g-C3N4: An effective photocatalyst for hydrogen evolution without a
co-catalyst, Nanomaterials 12 (5) (2022) 849.
[382] X. Zhang, H. Liang, C. Li, J. Bai, 1D CeO2/g-C3N4 type-II heterojunction for
visible-light-driven photocatalytic hydrogen evolution, Inorg. Chem. Commun.
144 (2022), 109838.
[383] Z. Chen, F. Guo, H. Sun, Y. Shi, W. Shi, Well-designed three-dimensional
hierarchical hollow tubular g-C3N4/ZnIn2S4 nanosheets heterostructure for
achieving efficient visible-light photocatalytic hydrogen evolution, J. Colloid
Interface Sci. 607 (2022) 1391–1401.
[384] M.A. Alcudia-Ramos, M.O. Fuentez-Torres, F. Ortiz-Chi, C.G. Espinosa-González,
N. Hernández-Como, D.S. García-Zaleta, M.K. Kesarla, J.G. Torres-Torres,
V. Collins-Martínez, S. Godavarthi, Fabrication of g-C3N4/TiO2 heterojunction
composite for enhanced photocatalytic hydrogen production, Ceram. Int. 46
(2020) 38–45.
[385] T. Feng, J. Jin, Y. Cao, H. Li, B. Dong, L. Cao, A novel CoSeO3 photocatalyst
assisting g-C3N4 in enhancing hydrogen evolution through Z scheme mode, Int. J.
Hydrogen Energy 47 (2022) 5999–6010.
[386] Z. Bi, R. Guo, X. Ji, X. Hu, J. Wang, X. Chen, W. Pan, Direct Z-scheme CoS/g-C3N4
heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen
generation, Int. J. Hydrogen Energy 47 (2022) 34430–34443.
[387] N. Arif, Z. Wang, Y. Wang, Y. Dou, K. Li, S. Liu, F. Liu, Design of earth-abundant Z-
scheme g-C3N4/rGO/ FeOOH ternary heterojunctions with excellent
photocatalytic activity, CrystEngComm 23 (2021) 1991–1998.