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Applied Surface Science


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A review on g-C3 N4 -based photocatalysts


Jiuqing Wen a , Jun Xie a , Xiaobo Chen b, , Xin Li a,
a
College of Materials and Energy, Key Laboratory of Energy Plants Resource and Utilization, Ministry of Agriculture, Key Laboratory of Biomass Energy of
Guangdong Regular Higher Education Institutions, South China Agricultural University, Guangzhou, 510642, PR China
b
Department of Chemistry, University of Missouri Kansas City, Kansas City, MO, 64110, USA

a r t i c l e

i n f o

Article history:
Received 23 May 2016
Received in revised form 2 July 2016
Accepted 3 July 2016
Available online xxx
Keywords:
Carbon nitride (g-C3 N4 )
Composite photocatalysts
Co-catalysts
Articial photosynthesis
Z-scheme heterojunction
Nanocarbons

a b s t r a c t
As one of the most appealing and attractive technologies, heterogeneous photocatalysis has been utilized
to directly harvest, convert and store renewable solar energy for producing sustainable and green solar
fuels and a broad range of environmental applications. Due to their unique physicochemical, optical and
electrical properties, a wide variety of g-C3 N4 -based photocatalysts have been designed to drive various reduction and oxidation reactions under light irradiation with suitable wavelengths. In this review,
we have systematically summarized the photocatalytic fundamentals of g-C3 N4 -based photocatalysts,
including fundamental mechanism of heterogeneous photocatalysis, advantages, challenges and the
design considerations of g-C3 N4 -based photocatalysts. The versatile properties of g-C3 N4 -based photocatalysts are highlighted, including their crystal structural, surface phisicochemical, stability, optical,
adsorption, electrochemical, photoelectrochemical and electronic properties. Various design strategies
are also thoroughly reviewed, including band-gap engineering, defect control, dimensionality tuning,
pore texture tailoring, surface sensitization, heterojunction construction, co-catalyst and nanocarbon
loading. Many important applications are also addressed, such as photocatalytic water splitting (H2
evolution and overall water splitting), degradation of pollutants, carbon dioxide reduction, selective
organic transformations and disinfection. Through reviewing the important state-of-the-art advances
on this topic, it may provide new opportunities for designing and constructing highly effective g-C3 N4 based photocatalysts for various applications in photocatalysis and other related elds, such as solar
cell, photoelectrocatalysis, electrocatalysis, lithium battery, supercapacitor, fuel cell and separation and
purication.
2016 Elsevier B.V. All rights reserved.

1. Introduction
Nowadays, among the various possibilities for exploring attractive sustainable energy sources and technologies, photocatalytic
technology is considered as one of the most appealing and promising technologies to directly harvest, convert and store renewable
solar energy for generating sustainable and green energy and
a broad range of environmental applications. In 1972, the pioneering work of photoelectrochemical (PEC) H2 production from
water splitting using a Pt-attached n-TiO2 cell was rstly reported
by Fujishima and Honda [1]. Subsequently, Bard extended the
basic principle of PEC water splitting system to the heterogeneous photocatalytic systems with illuminated semiconductor
particles suspended in water as photocatalysts [25]. Since then,

Corresponding authors.
E-mail addresses: chenxiaobo@umkc.edu (X. Chen), Xinliscau@yahoo.com
(X. Li).

the heterogeneous photocatalysis occurring on powdered semiconductors has been widely used in the different elds, such
as water splitting [610], environmental remediation [9,1115],
CO2 reduction [1620], disinfection [21] and selective organic
transformations[2224]. It is noteworthy that there has been a
growing interest in the use of semiconductors as photocatalysts
for various applications (the red columns in Fig. 1a). In 2015, more
than 5500 papers about the photocatalytic applications have been
published, further indicating the high importance and tremendous research interests in heterogeneous photocatalysis. Clearly,
the presence of efcient photocatalysts plays an essential role
in determining the overall quantum efciency of all these photocatalytic reaction systems. During the past 40 years, various
available semiconductor materials such as TiO2 , SrTiO3 , CdS, BiVO4 ,
Ta3 N5 , TaON, g-C3 N4 , Ag3 PO4 , and their nanostructured assemblies
have been extensively employed as photocatalysts to directly harness solar energy for different redox reactions [7,2530]. As the
most widely employed golden photocatalyst, TiO2 has dominated
the published work on heterogeneous photocatalysis owing to its

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Fig. 1. (a) The annual number of publications containing the word graphene* (TiO2 *, g-C3 N4 * or carbon nitride*) in the title and photocataly* in the topic since 2009. (b)
The annual number of citations for Wangs pioneering paper published on Nature Materials in 2009. (Using Web of Science, date of search: Jul 2, 2016).

chemical stability, high chemical inertness, nontoxicity, and low


cost [3136], which accounts for three-fths of all photocatalytic
research (the green columns in Fig. 1a). However, the large bandgap
of anatase TiO2 (3.2 eV) restricts the utilization of broad spectrum
of solar light (only utilization of the ultraviolet (UV) light in the sunlight, accounting for only 4% of the incoming solar spectrum), thus
leading to much lower quantum efciencies in using the solar spectra. To enhance the photocatalytic efciency of titania under visible
light (about 43% of the sunlight), a variety of modication strategies,
including doping, surface sensitization, nanostructuring, introducing defects or amorphous disorder layers, loading co-catalysts,
coupling with carbon and other semiconductors, have been utilized
to overcome the TiO2 materials-related issues and limitations, such
as the control of the band gap, band structure, optical properties and
available surface area for photo-induced reactions [7,25,3440].
Up to now, no one robust and commercially available material
could meet all requirements, such as high visible-light quantum
efciency, stability, safety and cheapness [7,41]. Thus, to tackle
these challenges, it is highly desirable to search for novel visiblelight-driven semiconductor materials and further fabricate highly
efcient systems/architectures for energy supply and environmental remediation.
The graphite-like carbon nitride (g-C3 N4 ), as a metal-free polymer n-type semiconductor, possess many promising properties,
such as unique electric, optical, structural and physiochemical
properties, which make g-C3 N4 -based materials a new class of
multifunctional nanoplatforms for electronic, catalytic and energy
applications [42,43]. Especially, g-C3 N4 -based photocatalysts have
attracted increasing interest worldwide, since Wang and his
coworkers rst discovered the photocatalytic H2 and O2 evolution
over C3 N4 in 2009 [44]. Clearly, the annual number of citations for
Wangs pioneering paper published on Nature Materials in 2009
signicantly increases every year (as shown in Fig. 1b). Thus, the
g-C3 N4 -based nanostructures are emerging as ideal candidates for
a variety of energy and environmental photocatalytic applications,
such as photocatalytic water reduction and oxidation, degradation
of pollutants and carbon dioxide reduction [27,4557]. More interestingly, as observed from Fig. 1b, although the annual number of
publications about g-C3 N4 -based photocatalysts is much smaller
than that about TiO2 photocatalysts, the publications of g-C3 N4
photocatalysis present an obvious approach to those of graphenebased photocatalysis [26,58]. More interestingly, the g-C3 N4 -based
photocatalysts together with the graphene-based ones are significantly reducing the proportion of TiO2 photocatalysts (as shown
in Fig. 1a). Absolutely, the g-C3 N4 , as the very exciting sustainable
material, has become a shining star in the photocatalytic eld.
Interestingly, as a novel metal-free polymeric semiconductor, gC3 N4 was quite different from most other semiconductors, which
could also be readily utilized to form various highly tailorable
hybrid photocatalysts with controllable compositions, sizes, thick-

ness, pore structures, size distributions, and morphologies. Hence,


it is of great interest to develop g-C3 N4 -based photocatalysts for
various applications through suitable modication, which is still
considered as a research topic of scientic and technological signicance in the elds of energy and environmental chemistry.
Importantly, many signicant and major breakthroughs have been
achieved in the synthesis and application of g-C3 N4 -based photocatalysts. In particular, many novel nanostructured g-C3 N4 -based
photocatalysts, including 1D nanorods, 2D nanosheets and 3D hierarchical structures, have been extensively developed in the past
several years due to their favorable absorption of solar radiation, efcient separation of charge carriers, high surface areas and
exposed reactive sites.
In fact, several excellent reviews are already available that focus
on the synthesis and modication of g-C3 N4 -based photocatalysts
and their applications in solving the energy and environmental
issues [27,4557,59]. However, only a handful of reviews have
focused on the versatile properties and rational design of g-C3 N4 based photocatalysts. Thus, it seems timely to offer a relatively
comprehensive and fully updated review on the state-of-the-art
advances of g-C3 N4 -based photocatalysts for heterogeneous photocatalysis. In the present Review, we devote our attention to
fundamentals, versatile properties, rational design and potential
applications of g-C3 N4 photocatalysts. We believe that this review
will not only promote the further developments of new g-C3 N4 based materials and architectures with improved utilization of
solar energy and photocatalytic efciency, but also could therefore
help to address the challenges for the widespread use of g-C3 N4 based photocatalysts in the renewable and sustainable energy
production and storage. It is also hoped that this review can provide some new ideas to develop new materials and architectures
for the other sustainable energy-related elds such as solar cells
[42,43,60,61], light emitting devices [62,63], fuel cells [6469], batteries [7075] and sensing devices [7682].

2. Fundamentals of g-C3 N4 -based photocatalysts


2.1. Mechanism of heterogeneous photocatalysis
So far, the fundamental mechanism of heterogeneous photocatalysis has been well proposed, as shown in Fig. 2. Basically
speaking, the heterogeneous photocatalysis involves seven key
stages, which could be usually classied into four major processes:
light harvesting (stage 1); charge excitation (stage 2); charge separation and transfer (stages 3, 4 and 5) and surface electrocatalytic
reactions (stages 6 and 7). Firstly, it is known that the light harvesting process (stage 1) is strongly dependent on the surface
morphology and structure of photocatalysts, which can usually
be signicantly improved through constructing the hierarchical
macroporous or mesoporous architectures, due to more efcient

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Table 1
Band gap structures of several typical photocatalysts.
Semiconductor

TiO2
Cu2 O
CdS
g-C3 N4
g-C3 N4
Ta3 N5
TaON
BiVO4
WO3
Ag3 PO4
a

Crystal structure

Anatase

cubic

Band Gap Structure (PH = 7,vs NHE)

Ref.

CB

VB

Eg /eV

0.5
1.16
0.9
1.3
1.53
0.75
0.75
0.3
0.1
0.04

2.7
0.85
1. 5
1.4
1.16
1.35
1.75
2.1
2.7
2.49

3.2
2.0
2.4
2.7
2.7
2.1
2.5
2.4
2.8
2.45

[90]
[91]
[92]
[44,84]
[93]a
[94]
[94]
[95]
[96]
[97]

Measurement by the valence band X-ray photoelectron spectroscopy (VB XPS) spectrum.
Table 2
Standard redox potentials for some typical species [83,98].

Fig. 2. The fundamental mechanism of heterogeneous photocatalysis. The typical


stages: (1) light harvesting; (2) charge excitation; (3) charge separation and transfer; (4) bulk charge recombination; (5) surface charge recombination; (6) surface
reduction reactions; and (7) surface oxidation reactions.

utilization of light through its multiple reections and scattering


effects [83]. At this regard, the at and smooth surface of 2D gC3 N4 is unfavorable for improving the light harvesting. Secondly,
the charge excitation of a semiconductor is strongly associated
with its unique electronic structures. Generally, an electron in the
VB of the semiconductor could be thus excited to its CB under
the light irradiation with energy higher than or equal to its band
gap energy (Eg ), leaving a positive hole in the VB. The band gap
structures of several typical photocatalysts were summarized in
Table 1. As observed in Table 1, as compared to TiO2 , BiVO4 and
WO3 , g-C3 N4 has the most negative CB level (1.3 V vs NHE at pH
7) and a medium band gap (2.7 eV) [44,84], facilitating its wide
application in visible-light photocatalysis. Thus, to achieve more
utilization of visible light, the band gap of g-C3 N4 should be further
narrowed by facile doping, defect and other possible sensitization
strategies [7]. Thirdly, the unfavorable charge recombination in
the bulk (stage 4) and on the surface (stage 5) of a semiconductor is detrimental to the charge separation and transfer (stage 3) to
surface/interface active sites, which has been regarded as the decisive factor for determining the photocatalytic quantum efciency.
Usually, shortening the diffusion length of photo-generated charge
carriers or constructing interfacial electric elds could efciently
reduce the recombination rates, thus substantially enhancing the
photocatalytic activity [7,85,86]. Finally, it is clear that only energetic enough electrons and holes that migrate to the surface of
the semiconductor without recombination can be trapped by the

Reaction

E0 (V) vs NHE at pH 0

2H+ + 2e H2 (g)
O2 (g) + e O2 (aq)
O2 (g) + H+ + e HO2 (aq)
O2 (g) + 2H+ + 2e H2 O2 (aq)
2H2 O (aq) + 4 h+ O2 (g) + 4H +
OH + h+ OH
O3 (g) + 2 H+ + 2 e O2 (g) + H2 O
CO2 + e CO2
2 CO2 (g) + 2 H+ + 2 e HOOCCOOH(aq)
CO2 (g) + 2H+ + 2e HCOOH(aq)
CO2 (g) + 2 H+ + 2e CO(g) + H2 O
CO2 (g) + 4H+ + 4e C(s) + 2H2 O
CO2 (g) + 4H+ + 4e HCHO(aq) + H2 O
CO2 (g) + 6H+ + 6e CH3 OH(aq) + H2 O
CO2 (g) + 8H+ + 8e CH4 (g) + 2H2 O
2CO2 (g) + 8H2 O + 12e C2 H4 (g) + 12OH
2CO2 (g) + 9H2 O + 12e C2 H5 OH(aq) + 12OH
3CO2 (g) + 13H2 O + 18e C3 H7 OH(aq) + 18OH
H2 O2 (aq) + H+ + e H2 O + OH
HO2 + H+ + e H2 O2 (aq)
H2 O2 (aq) + 2H+ + 2e 2H2 O

0
0.33
0.046
0.695
1.229
2.69
2.075
1.9
0.481
0.199
0.11
0.206
0.07
0.03
0.169
0.07
0.08
0.09
1.14
1.44
1.763

surface active sites or co-catalysts, and further stimulate the elctrocatalytic reduction (stage 6) and oxidation (stage 7) reactions of the
reactants adsorbed on the semiconductor, respectively. It should
be noted that the surface reactions possibly occur only when the
reduction and oxidation potentials are more positive and negative
than CB and VB levels, respectively. Some typical standard redox
potentials have been listed in Table 2. Notably, almost all reactions in Table 2 exhibit the same linear pH dependence with a
slope of 0.059 V, apart from E0 (O2 /O2 ) which is pH-independent
[83,87]. Furthermore, for the surface electrocatalytic reactions (surface charge utilization), the large onset overpotential and sluggish
kinetics are two key factors limiting the surface photocatalytic
efciency of reduction and oxidation reactions. Principally, these
two restrictive factors can be overcome by loading suitable cocatalysts (electrocatalysts) simultaneously [88]. More importantly,
the co-catalysts (electro-catalysts) can play the additional roles in
improving the photostability and charge separation of semiconductors [89]. The complicated co-catalyst effects will be thoroughly
discussed in the section 4.7.
However, it should be noteworthy that the photocatalytic quantum efciency (c ) is strongly determined by the cumulative effect
of the efciency in all four-step processes, including light harvesting efciency (abs ), charge separation efciency (cs ), charge
migration and transport efciency (cmt ), and charge utilization
efciency (cu ) for H2 generation. The relationship between them
could be expressed according to Eq. (1) [7]:
c = abs cs cmt cu

(1)

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Fig. 3. The redox potentials of the relevant reactions with respect to the estimated position of the g-C3 N4 band edges at pH 7.

Therefore, to design highly efcient photocatalysts for various


photocatalytic applications, all these typical four-step processes
must be comprehensively considered and optimized. Despite the
signicant advances in heterogeneous photocatalysis, there are
still many challenges related to the further enhancements of
light harvesting (especially for the visible light region), charge
carrier excitation, separation and utilization. In order to solve
these key scientic problems, a variety of engineering modication strategies have been proposed and applied in improving
the visible-light photocatalytic performances of heterogeneous
semiconductor materials, such as band structure engineering,
micro/nano engineering, bionic engineering, co-catalyst engineering, surface/interface engineering and their synergistic effects [7].
The detailed modication strategies and rational design on g-C3 N4 based photocatalysts will be thoroughly discussed in section 4.
2.2. Advantages and challenges of g-C3 N4 -based photocatalysts
Based on the above mechanism analysis, it is clear that the
band-gap and nano structures are crucial for their photocatalytic
applications. The band gap structures of g-C3 N4 , as well as some
standard potentials of typical redox reactions at pH 7 are illustrated
in Fig. 3. Clearly, as shown in Fig. 3, g-C3 N4 has a moderate band
gap of 2.7 eV, corresponding to an optical wavelength of 460 nm,
which makes it active under visible light. Considering thermodynamic losses and overpotentials in the photocatalytic process, the
band gap of 2.7 eV accidentally lies in between 2 eV and 3.1 eV,
thus achieving both the water-splitting with enough endothermic driving forces (much larger than 1.23 eV) and light absorption
in the visible range (smaller than 3.1 eV) [7]. More importantly,
g-C3 N4 also has a suitable CB position for various reduction reactions. It is noted form Fig. 3 that the favorable level of top CB of
g-C3 N4 is much more negative than those of conventional inorganic semiconductor counterparts in Table 1 and the potentials
of H2 -evolution, CO2 -reduction and O2 -reduction reactions, suggesting that the photo-generated electrons in g-C3 N4 possess a
large thermodynamic driving force to reduce various kinds of small
molecules, like H2 O, CO2 and O2 . As a consequence, the appropriate
electronic band structures of g-C3 N4 are favorable for its extensive
applications in wide areas, such as photocatalytic water splitting,
CO2 reduction, pollutant degradation, organic synthesis and disinfection.
Apart from the simplest and straightforward advantage of suitable optical band gap and position, it is widely accepted to date
that this metal-free g-C3 N4 material also possesses a stacked 2D
layered structure, in which the single-layer nitrogen heteroatomsubstituted graphite nanosheets, formed through sp2 hybridization
of C and N atoms, are bound by van der Waals forces, only (as
shown in Fig. 4a) [99]. Ideally, condensed g-C3 N4 consists of only
two earth-abundant elements: C and N, with a C/N molar ratio

Fig. 4. Fabrication strategies of g-C3 N4 and N-rich precursors.

of 0.75, suggesting that g-C3 N4 could be readily fabricated at low


cost. It also turned out that the g-C3 N4 has the advantages of biocompatibility and nontoxicity. Surprisingly, the viability activity
of HeLa cells could be maintained in the aqueous solution of gC3 N4 nanosheets with a concentration of up to 600 mg mL1 [100].
Furthermore, g-C3 N4 could be readily fabricated through the traditional thermal condensation of several low-cost N-rich organic
solid precursors such as urea, thiourea, melamine, dicyandiamide,
cyanamide, and guanidine hydrochlorid, at 500600 C in air or
inert atmosphere (Fig. 4) [27,101]. However, the disordered and
defective g-C3 N4 structures could be fabricated due to the incomplete removal of intermediates. Thus, the crystalline and condensed
g-C3 N4 can be readily prepared by other various fabrication strategies, including the ionothermal synthesis (molten salt strategy)
[102106], molecular self-assembly [107111], microwave irradiation [112,113] and ionic liquid strategy [114117] (Fig. 4).
In addition, the above three obvious advantages, as well as
several other advantages of g-C3 N4 , including the rich surface
properties, non-toxicity, abundance, and good stabilities, are summarized in Fig. 3, all of which give access to a wide variety of
applications [48]. All these features principally already allow its
direct use in sustainable chemistry as a multifunctional heterogeneous metal-free photocatalyst.
Unfortunately, the bulk g-C3 N4 generally exhibits the low photocatalytic efciency, due to some serious drawbacks of g-C3 N4
material itself. Specically, we will highlight several prominent
challenges of g-C3 N4 itself here: the high electronhole recombination rate, insufcient visible absorption (below 460 nm), low
surface area of g-C3 N4 (10 m2 /g, the high degree of conden-

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Table 3
Structural parameters and total energies for different C3 N4 phases [131].
C3 N4 phases

Space group

Lattice parameter ()

GW approximation band gap (eV)

local density approximation band gap (eV)

Alpha
Beta
Cubic
Pseudocubic
g-h-triazine
g-h-heptazine
g-o-triazine

P31 c (159)
P3 (143)
I-43d (220)
P42 m (111)
P-6m2 (187)
Cmc21 (36)
P2 mm (25)

a = 6.465, c = 4.709
a = 6.406, c = 2.406
a = 5.411
a = 3.426
a = 4.746, c = 6.586
a = 7.083, b = 12.269, c = 6.871
a = 4.147, b = 4.754, c = 6.474

4
2
2
1
2
4
2

5.49
4.85
4.30
4.13
2.97
2.88
0.93

3.76
3.12
2.87
2.53
1.16
0.89

composition, structures and properties. More denitely speaking, hetero-junction construction [120,121], dimensionality tuning
(nano-templating [122,123]) and nanocarbon loading have been
widely applied in promoting the charge transfer, mobility and
separation respectively. Furthermore, suitable co-catalyst loading
[44,124127] and defect control have been available in accelerating
the surface reaction kinetics (charge utilization). In addition, pore
texture tailoring, surface sensitization, and band-gap engineering (non-metal doping [128] and co-polymerization [84,129,130]
strategies) were utilized to create highly mesoporous g-C3 N4 with
high surface area and to increase the light harvesting and visible absorption through the red-shift of its optical absorption edge,
respectively. In future, it is expected more and more engineering
modication strategies will be developed to improve the photocatalytic performances of g-C3 N4 -based photocatalysts. More
importantly, all different photocatalytic stages such as light harvesting, charge excitation, charge transfer, mobility and separation,
and surface charge utilization should be simultaneously considered and optimized [7]. In other words, the synergy and integration
effect of these different strategies should be paid more attention.
In the following sections, the versatile properties, design strategies
and potential applications will be thoroughly summarized.
Fig. 5. Design considerations of g-C3 N4 -based photocatalysts based on the different
photocatalytic stages.

sation of the monomers) and small active sites for interfacial


(photo)reactions, slow surface reaction kinetics, moderate oxidation ability, grain boundary effects and low charge mobility which
disrupt the delocalization of electrons [51,118]. Additionally, it
should be noted from Fig. 3 that the photo-generated holes of
C3 N4 with moderate oxidation ability can only achieve oxygen
evolution from water oxidation, instead of the formation of the nonselective hydroxyl radicals, OH. At this point, the g-C3 N4 -based
photocatalysts seem to be a suitable candidate for selective photooxidation and related transformations of organic compounds in
aqueous media, avoiding the direct mineralization to CO2 by the
strong OH [119]. Thus, it is therefore highly desirable to lower
the top level of VB of C3 N4 to enhance its water oxidation power,
as 4-electron water oxidation reaction oxidation to O2 is a more
challenge half-reaction for water splitting. Although these prominent challenges of g-C3 N4 itself greatly limit its photocatalytic
performance enhancements, they also afford more opportunities to
construct more efcient g-C3 N4 -based photocatalysts in the future
studies.
2.3. Design considerations of g-C3 N4 -based photocatalysts
For these above reasons, careful consideration must be given
to the rational design of g-C3 N4 for achieving the optimum
photocatalytic performances. To avoid some of these drawbacks
and maximize the photocatalytic efciency, several modication strategies have been pursued to design highly efcient
g-C3 N4 -based photocatalysts. Fig. 5 summarizes the design considerations of g-C3 N4 -based photocatalysts based on their detailed

3. Versatile properties of g-C3 N4 -based photocatalysts


As is known, the photocatalytic efciency of g-C3 N4 -based photocatalysts is mainly governed by all parameters/properties of
g-C3 N4 itself, including crystal structural, surface physicochemical,
stability, optical, adsorption, electrochemical, photoelectrochemical and electronic properties. Thus, a fundamental understanding
and deterministic control of these chemical and structural factors
will enable the scalable production of g-C3 N4 -based composite
photocatalysts with the best photocatalytic behavior, which will be
favorable for creating some robust g-C3 N4 -based material systems
for practical photocatalytic applications and fundamental insights
into photocatalytic enhancement mechanisms at the single-atom
level.
3.1. Crystal structural properties
It is known that C3 N4 possesses seven different phases, e.g.,
-C3 N4 , -C3 N4 , cubic C3 N4 , pseudocubic C3 N4 , g-h-triazine, g-hheptazine and g-o-triazine, which exhibit the band gaps of 5.49,
4.85, 4.30, 4.13, 2.97, 2.88 and 0.93 eV, respectively, in terms of GW
method (as shown in Table 3) [131]. Among them, the famous super
hard -C3 N4 crystalline phase has been demonstrated to possess
the similar hardness/low compressibility to that of diamond [132].
Except the pseudocubic and g-h-triazine phases, other ve phases
have indirect band gaps in their bulk structures [127,131,133].
As observed from Table 3, it is clear that g-h-triazine and g-hheptazine phases exhibit the suitable band gaps of 2.97 and 2.88 eV
for visible-light absorption, favoring their applications in different photocatalytic elds. More interestingly, g-C3 N4 also shows
the stacked 2D layered structure, as displayed in Fig. 6a. Furthermore, two different condensation states have been demonstrated

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Fig. 6. The stacked 2D layered structure of g-C3 N4 (a); structures of s-triazine (b) and tri-s-triazine (c) as the primary building blocks of g-C3 N4 .

Fig. 7. XRD patterns of (a) the tubular carbon nitride and (b) the bulky g-C3 N4
synthesized by directly heating melamine at 520 C for 2 h [138].

as the primary building block in a single layer of g-C3 N4 networks:


s-triazine units (ring of C3 N3 ; Fig. 6b) with a periodic array of single
carbon vacancies; and tri-s-triazine/heptazine subunits (triring of
C6 N7 ; Fig. 6c) connected through planar tertiary amino groups with
larger periodic vacancies in the lattice [134]. More importantly, it
has been experimentally and theoretically demonstrated that the
energetically favored tri-s-triazine-based g-C3 N4 was 30 kJ mol1
more stable than the triazine-based g-C3 N4 , adequately suggesting that tri-s-triazine is the most widely accepted basic unit for the
g-C3 N4 networks [131,134136].
It is known that XRD has been extensively employed to precisely measure the lattice constant and crystal structures. The
typical experimental XRD pattern of bulky g-C3 N4 powders have
two distinct diffraction peaks located at 27.40 and 13.0 (as shown
in Fig. 7b), which can be indexed as (002) and (100) diffraction
planes for graphitic materials (JCPDS 87-1526) [44]. Clearly, the
XRD results indicate that the g-C3 N4 exhibits the ake-like structure with interplanar stacking distance of 0.325 nm revealed by
(002) diffraction, which is similar to that of graphite with stacking
distance of 0.34 nm [102,137]. The distance of 0.681 nm for in-plane
structural packing motif is slightly smaller than that of the tris-striazine units (ca. 0.73 nm), presumably due to the bending of 2D
layered structures [44]. However, the g-C3 N4 nanotubes exhibit one
distinct XRD diffraction peak at 17.4 (corresponding to an interplanar separation of d = 0.49 nm, Fig. 7a), indicating the formation of
the s-triazine units (with the theoretical value of d = 0.47 nm [127])
in g-C3 N4 [138]. Consequently, the exact periodic units in each layer

Fig. 8. Multiple functional surface properties of polymeric g-C3 N4 material with


defects [101].

of g-C3 N4 could be readily identied by the XRD peak associated


with an in-plane structural packing motif.
3.2. Surface physicochemical properties
It is known that a variety of surface defects on the surface of
polymeric g-C3 N4 material lead to the formation of multiple functionalities. Commonly, the basic primary and/or secondary amine
groups (e.g., CNH2 and C2 NH) on the terminating edges in the
single layer of g-C3 N4 (as shown in Fig. 8) could be created by
a small quantity of hydrogen impurity, owing to the incomplete
polycondensation [49,101]. Therefore, it is not surprising that the
g-C3 N4 materials with surface defects and electron-rich properties
also exhibit the unique nucleophilic character from basic surface
functionalities (for the activation of CO2 ) or H-bonding motifs (as
shown in Fig. 8), thus facilitating their more valuable applications
in catalysis, as compared to the ideal and defect-free g-C3 N4 [101].
Furthermore, it is easily understood that the abundant basic groups
( NH , N , NH2 and N C ) on the surface of g-C3 N4 are benecial for the removal of acidic toxic molecules through chemical
adsorption based on electrostatic interactions [139]. Similar to the
hydrophobic nature of the nanocarbon surface, hydrophobicity of
g-C3 N4 could lead to the formation of weakly interacted interfacial
layer, thus signicantly restricting the electron transport and separation and surface electrocatalytic reactions [61]. At this point, the
hydrophilicity of g-C3 N4 materials (with decreasing contact angle
of water on their surface) could be improved through introducing
oxygen-containing functional groups (hydroxyl and carboxyl) by

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Fig. 10. Comparison between the Raman spectra of coplanar bulk and 1-layer gC3 N4 samples (780 nm laser) [154].

Fig. 9. FTIR spectra of g-C3 N4 powders obtained by heating melamine (MCN),


thiourea (TCN), and urea (UCN) [146].

means of chemical oxidation, thus greatly favoring their good dispersion in the aqueous solutions and further enhanced interfacial
coupling and photocatalytic activities [140145].
Commonly, these functional groups and networks (C N ) could
be further identied by the Fourier transform infrared (FT-IR) spectra, X-ray photoelectron spectroscopy (XPS) measurements, Raman
spectra, and Boehm titration analysis. Generally, the chemical composition and bonding information of g-C3 N4 could be partially
identied by FT-IR measurement. Fig. 9 depicts typical FTIR spectra
of g-C3 N4 powders obtained by heating melamine (MCN), thiourea
(TCN), and urea (UCN) [146]. As shown, the main characteristic

peaks observed in the region from 900 to 1700 cm1 were usually
assigned to stretching vibration signals of aromatic heptazinederived repeating units, including the typical sp2 C N stretching
modes and out-of-plane bending vibrations of the sp3 C N
bonds [130,147150], while the sharp absorption peak centered
at approximately 810 cm1 was attributed to the characteristic
breathing mode of tri-s-triazine cycles [150152]. Meanwhile, the
absorption band at 883 cm1 were indexed as the deformation
mode of N H in amino groups [153], whereas the broadened
peaks between 3000 and 3500 cm1 were related to the stretching vibration [146,149,150,153] of residual free N H in the bridging
C NH C units and O H originated from physically adsorbed water
species on g-C3 N4 surface, respectively. In the recorded Raman
spectra, several characteristic peaks of g-C3 N4 can be observed
at 1616, 1555, 1481, 1234, 751, 705, 543, and 479 cm1 , further
conrming the vibration modes of CN heterocycles [151,154]. It
should be noted that the peak at 1234 cm1 , corresponding to
the N C (sp2 ) bending vibration, exhibits signicant blue shift
(1250 cm1 for 1-layer g-C3 N4 ), due to the phonon connement
and strong quantum connement effect [154]. Moreover, it has also
been experimentally and theoretically demonstrated that the ratios
of peak heights of 751705 cm1 (I751 /I705 ) and 543479 cm1
(I543 /I479 ), corresponding to layerlayer deformation vibrations or
the correlation vibrations, obviously increased with decreasing the
layer number of g-C3 N4 [154]. Additionally, the nitrogen containing species can be further quantitatively analyzed by the element
analysis and Boehm titration. For the element analysis, X-ray photoelectron spectroscopy (XPS) can not only reveal the atom ratio
of carbon to nitrogen, but also identify the carbon and nitrogen
species in g-C3 N4 . For example, the main peak at 288.2 eV in the
high-resolution C 1s XPS spectra of the 1.0 wt% RGO/g-C3 N4 sample, indicates the existence of the N C N2 coordination [151]. The
N 1 s binding energies at about 398.6, 399.8, and 401.5 eV in the
high-resolutionN1 s XPS spectra of the 1.0 wt% RGO/g-C3 N4 sample can be assigned to sp2 -hybridized nitrogen (C N C), tertiary
nitrogen (N (C)3 ) and amino functional groups having a hydrogen
atom (C N H), respectively [146,151,155,156]. For Boehm titration analysis, it was found that the content of basic group per unit
area of g-C3 N4 generally decreased with increasing the calcination
temperature [157]. In a word, the combination of Raman vibration properties, FTIR, XPS spectra and Boehm titration analysis can
fully reveal the surface functional groups of g-C3 N4 nanomaterials
(Figs. 9,10 and 11).
Interestingly, the basic surface functionalities can be further
evidenced by the isoelectric point (IEP) and the zeta potentials of
g-C3 N4 dispersions [146]. It is known that the IEP is an important
physicochemical parameter of many compounds, such as oxides,
suldes, hydroxides, and nitrides, which has been widely used
to estimate the surface charges of compound particles at various pH conditions. In general, the solid particles are positively

Fig. 11. High-resolution XPS spectra of C 1s (A) for the 1.0 wt% RGO/g-C3 N4 sample (a) and GO (b) and N 1s (B) for the 1.0 wt% RGO/g-C3 N4 sample [151].

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Fig. 12. Zeta potentials of MCN, TCN, and UCN powders as functions of the pH value
of the suspensions (as shown in Fig. 12) [146].

charged and negatively charged at pH values below and above the


IEP point, respectively. For example, Wang et al. found that the
zeta-potential of bulk g-C3 N4 dispersions in water was 47.4 mV,
showing a negative surface charge, whereas, g-C3 N4 exhibited a
positive surface charge with a zeta-potential of +30 mV after the
successful protonation in HCl solution [158]. Similarly, Yu and his
coworkers experimentally demonstrated that the IEPs of TCN, MCN,
and UCN samples are 4.4, 5.0 and 5.1, respectively, further conrming their basic and negatively charged surface. Thus, in the
initial pH, the MCN, UCN and TCN samples exhibited the negative Zeta potentials of 17.0, 30.7 and 19.9 mV, respectively (as
shown in Fig. 12) [146]. Thus, the surface protonation of g-C3 N4
treated by the acid solution with pH below its IEPs has become a
popular strategy to reverse the surface properties of g-C3 N4 from
negative to positive charge, facilitating the construction of composite materials through electrostatic interactions with negatively
charged materials and the enormous enhancement in photocatalytic performance [138,158162]. It was believed that surface
protonation modication could simultaneously achieve better dispersion, adjusted electronic band gaps, and increased surface area
and ionic conductivity [158]. In the contrary, the surface modication of g-C3 N4 via alkaline hydrothermal treatment (e.g. NaOH and
ammonium hydroxide) can create more surface hydroxylation and
rich surface H-bond network of g-C3 N4 with the negatively charged
surface, thus greatly enhancing the interfacial charge transfer, and
increasing the specic surface area and pore volume [163165].
Particularly, the H-bonding network can offer multiple channels
and inmate interfaces for the proton transfer from water to the
photo-excited electrons on g-C3 N4 surface, stabilize the negatively
charged intermediate and transition states, thus obviously promoting charge separation and photocatalytic H2 evolution [166].
3.3. Stability properties
The defect-rich and N-bridged tri-s-triazine-based g-C3 N4 was
found to be energetically favored relative to the other phases,
which exhibits extraordinary thermal stability up to 600 C
[149,167169]. In air, over a period of months, the stable g-C3 N4
only exhibited a slightly lighter color change, because of its strong
water adsorption effects [167]. Fig. 13 gives the thermogravimetricdifferential scanning calorimetry (TG-DSC) analysis for melamine
and g-C3 N4 prepared by heat polymerization of melamine at
520 C in air [149], which clearly indicated that the formation and
decomposition of g-C3 N4 (stable up to 600 C) involve a series
of processes, e.g., the sublimation and thermal condensation of
melamine (297390 C), de-ammonation process (545 C) and fur-

ther oxidation decomposition (630750 C) of g-C3 N4 material


[44,149]. It has been observed that melem transforms into a g-C3 N4
material by temperature-dependent X-ray powder diffractometry
investigations above 560 C [134]. The complete decomposition
temperature of g-C3 N4 ranging from 700 to 750 C, is in good
agreement with the Gillans report [167,170]. These typical processes were also observed during the formation of g-C3 N4 by using
cyanamide as precursors (as shown in Fig. 14), except for the rst
formation of melamine through condensing the cyanamide precursors [101]. Notably, the thermal stability of g-C3 N4 has been
regarded to be the highest in organic materials, which can be
obviously affected by the different polymerization degrees of gC3 N4 in different preparation methods [149,167,170173]. The
high thermal stability of g-C3 N4 polymeric semiconductor not only
features its various applications, as a heterogeneous organic catalyst, at operating temperature below 500 C, but also allows its easy
removal by simply increasing the calcination temperature beyond
600 C, thus favoring its utilization as connement templates, structuring agents or nitrogen sources for synthesizing a rened carbon
nanostructure or metal nitride nanostructures with continuously
adjustable composition, such as TaON, Ta3 N5 , ternary aluminum
gallium nitride and titanium vanadium nitride [55,174177].
Furthermore, the g-C3 N4 also exhibits superior chemical stability [167]. Similar to that of graphite, it has been demonstrated that
the g-C3 N4 with optimized van der Waals interactions between
the single layers is insoluble in water, acid, base, and various
kinds of organic solvents, including ethanol, toluene, diethyl ether
and THF [55,127,133,167]. However, notably, the molten alkali
metal hydroxides and KMnO4 could lead to the hydroxolysis and
the strong oxidation decomposition of intrinsic structures of the
g-C3 N4 materials, respectively [178]. In particular, the excellent
acid stability and interesting protonation effects have been also
further conrmed [178]. Commonly, the concentrated-acid treatment at room temperature could result in the formation of a
non-transparent solution containing highly dispersed nanosheets
without destroying the graphite-like structure of g-C3 N4 [158],
because the protonation effects could break both sheets and stacks
from its defects, as well as fabricate a highly porous texture
between the adjoining layers. Zhang et al. demonstrated that the
relatively good-quality g-C3 N4 thin lms could be fabricated by
conventional dip/disperse-coating techniques using a stable protonated g-C3 N4 colloidal suspension [179]. More recently, the rst
liquid state NMR spectra and a lyotropic liquid crystal phase of
g-C3 N4 have been successfully observed through the highly protonated g-C3 N4 thermodynamic solutions with concentration up
to 300 mg mL1 , highlighting the promising applications of g-C3 N4
solubilization technique in concentrated H2 SO4 [180].
3.4. Electronic properties
It is well known that the suitable electronic properties play
important roles in better photocatalysis. To look insight into
its electronic structure, the density-functional-theory (DFT) calculations were applied in obtaining the detailed oxidation and
reduction levels of valance and conduction bands. The results
shown in Fig. 15 demonstrated that the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO-LUMO)
gaps of melem molecule, polymeric melon and an innite sheet of
a hypothetically, fully condensed g-C3 N4 were 3.5, 2.6 and 2.1 eV,
respectively [44]. Clearly, the calculated band gap of polymeric
melon is very close to the experimentally measured medium-band
gap of 2.7 eV. The wavefunction investigations of the valence band
(Fig. 15b) and conduction band (Fig. 15c) are mainly derived from
nitrogen pz orbitals and carbon pz orbitals, which serve as oxidation
and reduction sites for O2 and H2 evolution reactions, respectively
[44]. Recently, it was found that, compared to the underestimated

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Fig. 13. The TG-DSC analysis for heating the melamine (a) and the g-C3 N4 (b) obtained by heat polymerization of melamine at 520 C [149].

Fig. 14. Reaction path for the formation of g-C3 N4 starting from cyanamide.

Fig. 15. Electronic structure of g-C3 N4 . (a) DFT band structure for g-C3 N4 calculated
along the X and Y directions. The potentials for H+ to H2 and H2 O to O2 are
displayed by the blue and red dashed lines, respectively; the KohnSham orbitals
for the valence band (b) and conduction band (c) of g-C3 N4 . The C, N and H atoms are
gray, blue and white, respectively. The isodensity surfaces are drawn for a charge
density of 0.01qe A3 [44]. (For interpretation of the references to colour in this
gure legend, the reader is referred to the web version of this article.)

band gaps of semiconductors and insulators calculated by density


functional theory (DFT) with local density approximation (LDA),
the band structures obtained by the GW approximation (larger
than the LDA band gap by 1.73 eV) are much more close to the
experimentally reported values [131].
Besides the DFT calculations, the band edge positions of g-C3 N4
materials can be determined by electrochemicalimpedance spectra (EIS), based on the MottSchottky (MS) plot, and the valence
band X-ray photoelectron spectra (VB-XPS), respectively [7]. Wang
and his coworkers measured the at band potentials of bulk gC3 N4 through the MS method, indicating that its conduction band
and valance band edges are located at 1.3 and 1.4 V vs NHE at
pH 7, respectively [54,84,187]. Meanwhile, Yan et al. obtained the
accurate conduction band and valance band edges of bulk g-C3 N4
located at 1.53 and 1.16 V vs NHE at pH 7 by the VB-XPS mehod,
respectively [93]. However, it is worthy of noting that these two
results seem to be slightly contradictory. The main reason is probably that many researchers directly equate the at-band potential
with the conduction band potential. In fact, for an n-type semiconductor, the conduction band potential is more negative by
about 0.1 or 0.2 V than the at-band potential [7]. Considering the slight difference (0.2 V) between the at-band potential
and the conduction band potential, there was complete agreement
between these two experimental results. The band structures of
different types of g-C3 N4 samples obtained by these two methods
have been summarized and listed in Fig. 16. As shown in Fig. 16, the
doping of P and C can make the conduction and valance band edges
of g-C3 N4 more negative and positive, respectively, thereby facilitating the reduction and oxidation reactions. In future, it is expected
that more accurate band positions of g-C3 N4 could be available and
applied in the design and development of highly efcient g-C3 N4 based photocatalysts.

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Fig. 16. Schematic illustration of the band structures of different types of g-C3 N4 samples: g-C3 N4 [84], Feg-C3 N4 [54,181], Sg-C3 N4 [182], Pg-C3 N4 [183], Og-C3 N4 [184],
Cg-C3 N4 [185], Ig-C3 N4 [186] and Bg-C3 N4 [84]. VB-XPS: valence band X-ray photoelectron spectroscopy; MS: electrochemical analysis by MottSchottky plots.

Fig. 17. (a), time-resolved PL spectrum monitored at 525 nm under 420 nm excitation at 298 K for bulk g-C3 N4 (black) and mpg-C3 N4 (red) [123];(b), time-resolved PL spectra
monitored at 480 nm under 420 nm excitation at 77 K for CN and CNSCN [121]. (For interpretation of the references to colour in this gure legend, the reader is referred to
the web version of this article.)

In addition, the underlying electronic properties and charge carrier dynamics, including the microscopic dynamic process of the
charge generation, recombination, separation, and transfer, play
crucial roles in determining the photocatalytic performance [7,58].
Thus, the in-depth understanding of the electrical properties and
charge carrier dynamics is, therefore, fundamentally important
to help us to design and construct the more efcient and stable
g-C3 N4 -based composite photocatalysts. To date, many different
advanced techniques, such as femtosecond transient absorption
(TA) spectroscopy [188,189], time-resolved uorescence spectroscopy, transient photocurrent decay, Nyquist impedance plots
and the transient photovoltage (TPV) technique [190195] have
been available in studying the charge carrier dynamics of g-C3 N4 based composite photocatalysts. For instance, Wang et. al measured
the time-resolved PL spectrum of bulk g-C3 N4 and revealed that the
photoinduced charge carriers in bulk g-C3 N4 showed a lifetime of
5 ns even at 298 K, indicating the fast recombination rate (Fig. 17a)
[123]. The greatly suppressed PL signal of mpg-C3 N4 further indicated that the surface terminal sites of mpg-C3 N4 can promote the
electron relocalization, thus accelerating the catalytic functions of
mpg-C3 N4 for surface redox reactions. Similarly, the isotype heterojunctions between g-C3 N4 and S-doped g-C3 N4 have been found to
exhibit a matched band alignment, which can signicantly promote
the charge separation between them, thus resulting in prolonging
the lifetime of photo-excited charge carriers by about 2.15 ns [121].
It is believed that the prolonged lifetime of photo-generated charge
carriers could further increase their utilization efciency in driving
surface photoredox reactions. Recently, the TA spectra of g-C3 N4
also revealed that the existence of silica templates can prolong the
lifetime of excited charge carriers by about hundreds of picoseconds, thereby achieving the high photocatalytic activities (Fig. 17b)
[188]. More recently, it was demonstrated that the charge separate
efciency in g-C3 N4 -based photocatalysts could be also revealed
by the SPV measurement, as an advanced and facile technology. As
shown in Fig. 18, the obviously increased SPV signal in the range

Fig. 18. SPV of g-C3 N4 (Ni0) and Ni@g-C3 N4 (Ni10). The inset shows the schematic
setup of SPV measurements [192].

of 300450 nm could be achieved through loading Ni nanoparticles on g-C3 N4 as co-catalysts, suggesting the greatly accelerated
charge separation efciency [192,193].
3.5. Optical properties
For various kinds of photochemistry-related applications of gC3 N4 , the decisive optical properties, including Ultravioletvisible
(UV/Vis) absorption, photoluminescence (PL) and electrochemiluminescence (ECL), have been readily further revealed by means
of the theoretical calculations or experimental characterizations
[47,55,187]. The typical UV/Vis absorption spectrum of g-C3 N4 prepared at different temperature were displayed in Fig. 19a [44].
Indeed, the absorption edge of conventional g-C3 N4 shows an

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Fig. 19. (a) UV/Vis absorption spectra of g-C3 N4 prepared at different temperature. Inset: photograph of the photocatalyst [44]; (b) the room-temperature PL spectrum
of g-C3 N4 solid powder ( = 365 nm, top gure) and the ECL spectrum of g-C3 N4 -modied electrode in 0.10 M K2 SO4 and 3.0 mM K2 S2 O8 solution by cycling the potential
between 0.00 and 1.30 V (vs. Ag/AgCl) with a scan rate of 100 mV/s and step potential of 1 mV (bottom gure) [78].

obvious red shift towards longer wavelengths with increasing


condensation temperatures, indicating that the increasing polymerization degrees can achieve a decreasing bandgap [44,196]. The
results are also consistent with those obtained by the theoretical
calculations. Furthermore, it can be seen that these two samples
fabricated at 550 and 600 C exhibit very similar strong bandgap
absorption, with edges at approximately 450 nm. The band gap
energy (Eg ) can be further obtained according to the intercept of
the tangents to the plots of (h)1/2 vs. photon energy [146,148].
The bandgap of the condensed g-C3 N4 prepared at 550 C is estimated to be 2.7 eV from its UVvis spectrum, in good agreement
with previous studies [148]. In fact, the greyish yellow color of gC3 N4 can further conrmed the favorable medium band gap for
visible light absorption, as observed in the inset of Fig. 19a. More
interestingly, other modication strategies, such as doping by Fe,
S, P, C, I, O and B atomics (as shown in [16]) and barbituric acid
moleculares [84] can also lead to a redshift of the adsorption edges.
Apart from UV/Vis absorption spectrum of g-C3 N4 , intensive
investigation also focus on its PL and ECL spectrum, due to its
semiconductor properties. Both PL and ECL spectrum of g-C3 N4
were also displayed in Fig. 19b [78]. As observed in Fig. 19b (top
gure), the room-temperature PL spectrum of g-C3 N4 solid powder at = 365 nm, exhibited a strong blue emission band ranging
from 400 to 650 nm, with a maximum peak of ca. 470 nm in the
blue region. It is generally believed that the intensity of roomtemperature PL signal is employed to directly and qualitatively
elucidate the recombination rate of photo-generated electrons and
holes in irradiated g-C3 N4 [155,156,197,198]. Commonly, lower
peak intensities imply the improved charge trapping and efciently transferring, thus further prolonging the lifetimes of charge
carriers and facilitating the enhancements in photocatalytic activity [199201]. It should be noted that the room-temperature PL
spectrum of g-C3 N4 nanosheets are sensitively and markedly determined by their condensation degree (or optical band gap), thickness
and sizes [47,100,202,203]. It was also observed in the bottom of
Fig. 19b that the g-C3 N4 -modied electrode in 0.10 M K2 SO4 and
3.0 mM K2 S2 O8 showed the slightly broader ECL spectrum, with a
maximum peak at ca. 470 nm (2.6 eV), which matches closely with
the room-temperature PL spectrum of g-C3 N4 solid powder. The
blue ECL emission from g-C3 N4 is strong enough to be observed
with naked eyes as shown in the inset of bottom Fig. 19b [78].
Although there are obvious differences between the excited state of
g-C3 N4 in ECL and the room-temperature PL spectrum, the similar
maximum emission peak of both types of luminescence suggested
that identical ECL emission is also attributed to the band gap luminescence [78]. The results clearly demonstrated that the g-C3 N4
semiconductor could be also a new kind of efcient and promising
luminophore for ECL sensing to achieve the sensitive and selective

detection of trace metal ions, such as Cu2+ . Therefore, it is naturally expected that the metal-free and non-toxic g-C3 N4 could be
extensively utilized as a multifunctional optical material for light
emitting devices [62,63], bioimaging, [100,142,204,205] ECL sensing probe [76,78,206,207] and uorescent probes [208210].
3.6. Adsorption properties
Generally speaking, adsorption property of a given adsorbent
is strongly dependent by both its porous microtexture and surface chemical property [211215]. Similar to the 2D graphene or
graphene oxide materials, a wide variety of targeted adsorbates
can be adsorpted on the multiple different functional groups (e.g.,
amino groups) and defect sites on g-C3 N4 through different types
of interactions such as physical adsorption (- stacking interaction), electrostatic attraction, or chemical interaction (surface
complexation or acid-base interactions) [216]. Due to the weaker
- stacking interaction in the physical adsorption, the stronger
electrostatic attraction and chemical interaction have been proposed to the improved adsorption properties of g-C3 N4 , which will
be thoroughly discussed in this section.
Based on the electrostatic attraction, it has been demonstrated
that the selective photodecomposition of anionic methyl orange
(MO) or cationic methyl violet (MV) and methylene blue (MB) could
be achieved over positively or negatively charged TiO2 -based semiconductors, respectively [217219]. Similarly, the electrostatic
attraction between the negatively charged g-C3 N4 and positively
charged adsorbate molecules, such as cationic MV and MB have
been proposed to achieve the selective adsorption and photocatalysis in many studies. For example, Yu and his coworkers
demonstrated that the negatively charged g-C3 N4 particles exhibited extraordinaryly higher adsorption capacity towards a cationic
MB dye than anionic MO dye in aqueous suspension [146]. Further results showed that the adsorption kinetics of MB on three
different kinds of g-C3 N4 (Fig. 20a) could be well depicted by a
pseudo-second-order kinetic equation as follows [220]:
dqt /dt = k2 (qe qt )2

(2)

t/qt = 1/(k2 qe 2 ) + t/qe

(3)

where qt (mg g1 ) is the adsorption amount at time t, and k2


(g mg1 min1 ) is the pseudo-second-order rate constant, and qe
(mg g1 ) is the maximum adsorption amount. Notably, it was
also revealed that the adsorption kinetics of heavy metal cationic
ions and peruorooctane sulfonate over g-C3 N4 also followed the
pseudo-second-order kinetic model [157,221]. Meanwhile, it can
be also found that the Langmuir model, as compared to Freundlich
model, could be used to better t the adsorption isotherms of MB

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Fig. 20. Adsorption kinetics (a) and adsorption isotherms (b) of methylene blue on MCN, TCN, and UCN [146].

on three g-C3 N4 samples (Fig. 20b), indicating the homogeneity of


the adsorbent surface [146]. Differences in the adsorption activity
of three samples towards MB can be attributed to the synergistic
effect of surface area and zeta potential.
Apart from the electrostatic attraction, the chemical interaction
(surface complexation or acid-base interactions) between g-C3 N4
and targeted adsorbates has been widely applied in manipulating the adsorption properties of g-C3 N4 . Fifty years ago, Pearson
rstly proposed the well-known hard and soft acids and bases
(HSAB) principle [222,223], stating that hard and soft acids will
interact preferentially with hard and soft bases, respectively. So
far, this principle has been widely employed to clarify the chemiadsorption interactions between various kinds of adsorbents and
adsorbates with different acidic and basic properties [224,225].
According to the HSAB principle, it is clear that the acidic molecules
such as CO2 , H2 S and NOx should be readily chemically bond
to the basic nitrogen-containing groups of g-C3 N4 . Recently, Oh
et al. demonstrated that the g-C3 N4 functionalized porous reduced
graphene oxide aerogel could achieve a large CO2 adsorption capacity (0.43 mmol g1 ) and high CO2 selectivity against N2 under
ambient conditions, and an easy regeneration of 98% adsorpted
CO2 by simple pressure swing [226]. Importantly, the DFT calculations further revealed that the strong dipole interaction induced
by electron-rich nitrogen at the microporous edges of g-C3 N4 is
the critical factor for achieving the high-capacity, regenerative and
selective CO2 capture. It is highly desired that the chemoselectivity of g-C3 N4 interactions for other gases could be also further
tailored through effectively developing the porous structure and
increasing the content of nitrogen-containing groups on the surface of g-C3 N4 [227]. For example, Jia et al. demonstrated that a
simple oxygen-atmosphere UV irradiation could create the sufcient acidic sites on hierarchically ordered macro-/mesostructured
g-C3 N4 lms, such as COOH and N-oxide groups through replacing
its surface basic nitrogen-containing groups, [228] thereby achieving the highly selective chemi-adsorption of basic molecules. In
the contrary, Yu and his coworkers demonstrated that the loading
of amine groups on g-C3 N4 through monoethanolamine solution
treatment can successfully achieved a 3.76-times enhancements
in the adsorbed CO2 amount, as compared that of pristine g-C3 N4
under ambient pressure and temperature (Fig. 21), owing to the
combination effects of both physical and chemical adsorption of
CO2 [227]. Importantly, it was also observed that the enhanced
adsorption and activation (favoring the formation of nonlinear
HCO3 ) of CO2 molecules over amine-functionalized g-C3 N4 were
benecial for the improvement of CO2 photoreduction efciency
and selective formation of CH4 [227]. More surprisingly, the CO2
adsorption capacity of g-C3 N4 microspheres with 3D hierarchical
pores and a much higher BET surface area (550 m2 /g) could reach
2.90 and 0.97 mmol/g at 25 and 75 C, respectively [229]. However, even so, the CO2 adsorption capacity is still obviously lower
than those of famous molecular basket adsorbents (133 mg/g)

[230232], activated carbon (3.75 mmol/g) [233] and metal organic


framework (35 mmol/g) [234236], implying there are still ample
room to enhance the CO2 adsorption capacity of g-C3 N4 semiconductor photocatalysts. In this end, the g-C3 N4 semiconductors with
rich basic nitrogen-containing groups, high surface areas, porous
structures and suitable band gaps seem to be very promising for
the applications in the eld of photocatalytic CO2 reduction, H2
evolution and the oxidation of NOx and H2 S, because porous g-C3 N4
could simultaneously serve as light-harvesting, charge-excitation,
charge-transportation, adsorption (for acid CO2 , H+ , NOx and H2 S
molecules) and catalytic centers [237].
3.7. Electrochemical properties
As shown in Fig. 2, the photocatalytic reduction and oxidation reactions on the surface of semiconductors are fundamentally
electrocatalytic ones driven by the photo-generated electrons and
positive holes, respectively. More interestingly, g-C3 N4 semiconductor itself can also serve as the multifunctional electrocatalysts
with higher activity than pure carbon [238,239], which play signicant roles in achieving the improved overall photocatalytic
efciency. Commonly, pyridinic N atoms of g-C3 N4 with strong
electron-accepting ability can serve as active sites for the electrochemical reactions, making it a potential metal-free electrocatalyst
[55]. Unfortunately, the moderate conductivity and poor electron
transfer ability of g-C3 N4 greatly limit its electrochemical performances and applications in various electrocatalysis elds, such
as O2 reduction reaction (ORR) for fuel cells [240] and H2 evolution reaction (HER) for water splitting [241]. Consequently, in the
past several years, extensive research efforts have been devoted
to the exploration of hybrid g-C3 N4 -based electrocatalysts with
higher electroconductivity and more active sites, through several
strategies, such as manipulating size, thickness and structure, coupling with various semimetal carbon materials and doping with
heteroatoms [242].
It has been well accepted that surface electrocatalytic ORR over
various heterogeneous semiconductors has been found to play
key roles in determining the photocatalytic activity of pollutant
degradation [20,25,243] and organic synthesis [244,245]. However,
so far, most of ORR co-catalysts loaded on the surface of semiconductors for photodegradation and photosynthesis are mainly
constituted of noble metal elements, such as Pt [246248], Au
[249,250] and Ag [251,252] nanoparticles/clusters. Fortunately, it
has been recently revealed that the N-doped nanpcarbon materials, such as N/S or B/N co-doped graphene [253,254], N-doped
graphene/porous carbon [255], Mn3 O4 /N-doped graphene [256]
and N-doped graphene (carbon spheres, nanoyubes or nanocages)
[257261], exhibited excellent electrocatalytic ORR activities for
direct methanol fuel cells (DMFC). More interestingly, it has been
demonstrated that the electrocatalytic 4e ORR activities of g-C3 N4
could be signicantly enhanced via the coupling with different

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Fig. 21. (a) CO2 -capture capacities of g-C3 N4 (CN) and amine-functionalized g-C3 N4 (3CN) [227]; (b) CO2 adsorption isotherms of the mesoporous g-C3 N4 microspheres at
25 and 75 C [229].

Fig. 22. (A), (a) Free energy plots of ORR on g-C3 N4 with 0e , 2e , and 4e paths (corresponding to paths I, II, and III). (bd), Schemes of ORRs pathway on pristine g-C3 N4
with 0e , 2e or 4e participation, respectively (red areas represent the active sites facilitating ORR). (B) ORR polarization curves for various electrocatalysts on rotating
electrode at 1500 rpm in O2 -saturated 0.1 M KOH solution [69]. (For interpretation of the references to colour in this gure legend, the reader is referred to the web version
of this article.)

kinds of conductive carbon support, owing to the improved electron


accumulation and transfer on the surface of g-C3 N4 . Accordingly,
the new-generation metal-free g-C3 N4 -carbon hybrid cathode
electrocatalysts in DMFC, could achieve both the superior electrochemical ORR efciency and the high CO/methanol tolerances
[48]. So far, various kinds of nanostructured g-C3 N4 -carbon hybrids,
such as g-C3 N4 @carbon [64,69], 2D g-C3 N4 nanosheet/1D carbon
nanotube [65], 2D g-C3 N4 nanosheets/graphene [66,262264], hollow mesoporous g-C3 N4 nanosphere/3D graphene [265], graphene
supported Co-g-C3 N4 [266] and g-C3 N4 @cobalt oxide[267] have
been extensively fabricated and demonstrated to be high-efciency
ORR electrocatalysts. For example, Qiao and coworkers theoretically revealed that the limited electron transfer ability of g-C3 N4
leads to the low ORR catalytic activity of pure g-C3 N4 through an
unfavorable 2e pathway (as shown in Fig. 22A) [69], whereas,
the accelerated electron transfer and increased active sites in the
nanoporous g-C3 N4 @carbon composite could achieve a nearly 100%
of selectivity for 4e ORR pathway in alkaline aqueous solution. The
further experimental results conrmed that the g-C3 N4 @ordered
mesoporous carbon (CMK-3) exhibited a considerably lower onset
potential and comparatively higher ORR current density, as compared to those of g-C3 N4 (m) and the g-C3 N4 /CMK-3 mixture
electrodes (as shown in Fig. 22B). By the same way, the hybrid of
g-C3 N4 and conductive metal has also been found to signicantly
improve its the sluggish cathodic ORR in fuel cells [241,268,269].
At this point, it is highly desired that more and more metalfree g-C3 N4 /carbon and earth-abundant metal/g-C3 N4 hybrid ORR
electrocatalysts could be exploited and utilized as co-catalysts to
greatly facilitate the photocatalytic activity of pollutant degradation and organic transformation.
Similar to the ORR, the thermodynamically uphill HER, as a central reaction in the electrochemical water splitting, always requires

suitable catalysts with high electrocatalytic activity and durability


to accelerate the sluggish kinetics. In contrast to most of Pt-free
electrocatalysts, the best-known heterogeneous Pt/C composite
has proven to be the most effective HER electrocatalyst, due to
their high exchange current density at low overpotentials, chemical
inertness, versatility, high conductivity, and resistance to oxidation
[270]. However, high cost and low abundance of the noble metal
Pt dramatically restricted its practical widespread applications.
Although the cheap and earth-abundant transition metals, such as
Fe, Co, Ni, W, Mo and their molecular derivatives, as Pts alternatives, have been found to display outstanding electrocatalytic
HER activity, their low stability in acidic and basic media are unfavorable for the long-term operation [88,124,242,271275]. In this
regard, metal-free g-C3 N4 /conductive carbon hybrids beyond metals have also shown great promise as attractive HER electrocatalysts
for water splitting reactions due to their earth abundance, tunable
molecular structures, the unique advantages to easily fabricated
a variety of nanostructures and strongly tolerance acid/alkaline
environments [239]. The theoretical calculations revealed that the
strong electronic coupling between g-C3 N4 and graphene could signicantly improve electron conductivity and optical absorption of
g-C3 N4 , thus leading to the greatly promoted charge separation
and transfer at the graphene/g-C3 N4 interface [276]. Subsequently,
Qiao and co-workers further experimentally veried that the asconstructed multilayered g-C3 N4 nanodomains on nitrogen doped
ultrathin graphene sheets (C3 N4 @NG) exhibited superior HER
activity, achieving a 10-mA cm2 HER current density at an overpotential of 240 mV (as shown in Fig. 23a) [239]. From the viewpoint
of thermodynamics, compared to too strong and weak chemical
adsorption of H* on g-C3 N4 and N-graphene with the Gibbs freeenergy of 0.54 and 0.57 eV (Fig. 23b), respectively, the C3 N4 @NG
hybrid with the Gibbs free-energy of about 0.19 eV, exhibits a medi-

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Fig. 23. (a) The HER polarization curves of g-C3 N4 , NG, g-C3 N4 /NG mixture, 33 wt% of g-C3 N4 @NG and referenced 20% Pt/C smaples (electrolyte: 0.5 M H2 SO4 , scan rate:
5 mV s1 ). (b) The calculated Gibbs free-energy for chemical adsorption of H* on three metal-free catalysts and Pt reference at the equilibrium potential. (c) Volcano plots of i0
as a function of the GH for the C3 N4 @NG (red triangle), various metals (open symbols) and a nanostructured MoS2 electrocatalyst (closed symbol) [239]. (For interpretation
of the references to colour in this gure legend, the reader is referred to the web version of this article.)

ated adsorptiondesorption behavior, facilitating the overall HER


kinetics. In additional, as displayed in the volcano plot (Fig. 23c), the
HER activity of metal-free C3 N4 @NG is very close to those of famous
MoS2 electrocatalysts. It was also demonstrated that the broken
N3C bonds at the edge of g-C3 N4 lead to the formation of defect
sites, pyridinic nitrogens, which could act as the stable H* adsorption sites and electrocatalytic HER active sites [239]. Inspired by
this interesting work, Qu and co-workers developed a more active
3D porous HER elctrocatalyst based on the hybrid of 1D g-C3 N4
nanoribbons and 2D graphene sheets, exhibiting a current density of 10 mA cm2 at an overpotential of 207 mV, in 0.5 M H2 SO4
solution [277]. It is believed that the high activity was attributed
to the increased proton binding sites on 1D g-C3 N4 nanoribbons,
close contact between g-C3 N4 and graphene, and unique 3D porous
networks for improved mass transfer and diffusion. More recently,
the supramolecular Cu-doped g-C3 N4 , as a biomimetic HER electrocatalyst, has been also demonstrated to show a high current
density of 10 mA cm2 at a low overpotential of 0.39 V in acidic
media [278]. Thus, developing the novel non-noble-metal g-C3 N4 based HER electrocatalysts with high stability and activity is still a
promising direction in the near future.

3.8. Photoelectrochemical properties


Besides direct utilization as electrocatalysts, g-C3 N4 has proven
to be a promising photoelectrode candidate for solar energy
conversion in the PEC cells, due to its superior chemical and
thermal stability and suitable electronic band structure. Initially,
Zhang and Antonietti rstly observed the maximum cathodic photocurrent response (up to ca. 50 mA cm2 at 0.3 V, IPCE 3% at
420 nm) of bulk mpg-C3 N4 lm in KCl aqueous solution containing Fe(II) ions, under visible light ( > 420 nm, 150 W Xe lamp)
[181]. The at band potential (Efb ) of different g-C3 N4 semiconductors can also be further estimated from the onset photocurrent
potential. More importantly, a tripled maximum photocurrent
was also observed for the binary composite lm of mpg-C3 N4
and standard Degussa P25 TiO2 (as the electron-transport channel) under the same conditions. However, the unfavorable factors
of bulk g-C3 N4 lm in this study, such as larger domain sizes,
grain boundary defects and textural effects, implying there is
still ample room to further optimize the g-C3 N4 photoelectrodes.
Similarly, the weak transient photocurrent response of different bulk or modied g-C3 N4 solids was extensively conrmed in
other works [84,114,123], which is generally used to identify the
enhanced photocatalytic activity and charge separation as an auxiliary tool. To further improved the PEC properties of g-C3 N4 lms
and extend their applications, various fabrication methods and
modication strategies of g-C3 N4 lms have been widely devel-

oped [43]. For example, Zhang et al. achievedan almost 3-fold


higher cathodic PEC activity for hydrogen evolution from water
than that of the pure g-C3 N4 through simultaneously fabricating
a sponge-like structure and incorporating active carbon-dopant
sites, under simulated solar-irradiation [279]. They attributed the
enhanced activity to the increased charge mobility, surface area,
mass transfer, active sites and -conjugated structure. Furthermore, the g-C3 N4 -based composite photoelectrode lms such as
g-C3 N4 /CuInS2 [280], TiO2 /g-C3 N4 [281283], CdS/g-C3 N4 [284],
g-C3 N4 /WO3 [285287], g-C3 N4 /N-doped graphene/NiFe-layered
double hydroxide [288], Fe2 O3 /g-C3 N4 [289], and g-C3 N4 /MoS2
[290], also exhibited signicantly enhanced PEC activity for hydrogen evolution or water oxidation, due to the promoted charge
separation, enhanced visible-light absorption, accelerated surface
reaction kinetics and suppressed photocorrosion. For example,
Feng and coworkers demonstrated that the as-fabricated WO3
nanosheet Array/g-C3 N4 /CoOx layered heterojunction photoanode
exhibited a photocurrent density of 3.61 mA cm2 at 1.6 V vs. NHE
(as shown in Fig. 24a) [285]. It is suggested that the increased
light-harvesting ability, unique 3D nanostructures with 2D layered
nano-junctions, accelerated water oxidation kinetics, and excellent charge transfer and separation are the possible reasons for the
enhanced PEC water-oxidation activity (as shown in Fig. 24b). Additionally, the g-C3 N4 -based lms have also been widely applied in
the PEC degradation of organic pollutants [291296]. Typically, Zhu
and coworkers demonstrated that the g-C3 N4 lm could achieve the
removal of 89.3% of the total organic carbon (TOC) under a 2.5 V bias,
which was 2.4 times higher than that of photocatalytic degradation [293]. It is believed that the dramatic enhancement in activity
can be attributed to the promoted activity of electrocatalytic (EC)
oxidation, improved charge separation, and increased reactive radical species, such as OH and O2 , due to the combination effects of
photocatalysis and electrocatalysis. Thus, in the near future, it is
naturally expected that the g-C3 N4 -based lms can be widely used
in more and more PEC elds, and their activity should be further
improved through better balancing electronic structures (e.g. bandgap and redox ability), stability, change-carrier mobility and active
sites, surface area.

4. Design strategies of g-C3 N4 -based photocatalysts


Although the multi-function properties endow g-C3 N4 a bright
future in the various kinds of photocatalytic applications, low quantum efciency limits its practical utilization in a large scale. To
date, tremendous efforts have been made to improve the photocatalytic efciency of g-C3 N4 through different design strategies,
including band-gap engineering, defect control, pore texture tailoring, dimensionality tuning, surface sensitization, heterojunction

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Fig. 24. (a) Variation of photocurrent density versus applied voltage. Number lables (3), (2), and (1) data represent the hybrid 3D WO3 /C3 N4 //CoOx , WO3 /C3 N4 , and WO3 ,
respectively. (b) Energy diagram and expected charge ow of WO3 /C3 N4 [285].

Fig. 25. Summary of band-gap engineering for g-C3 N4 .

construction, co-catalyst and nanocarbon loading, which will be


systematically discussed in this section.
4.1. Band-gap engineering
In general, it is known that the ideal bandgap of a semiconductor should be 2.0 eV, which could harvest a variety of visible
light to generate sufcient electrons and holes with strong driving forces for photocatalytic redox reactions [7,10]. However, the
2.7 eV bandgap of g-C3 N4 make it only utilize the solar light with
wavelength below 460 nm. Thus, in order to further enhance the
light harvesting ability of g-C3 N4 , various band-gap engineering
strategies, including atom-level (foreign metal and non-metal elements) and molecular-level (copolymerization) doping, have been
widely exploited and demonstrated to achieve the enhanced photocatalytic performance [27,54], which will be summarized in Fig. 25
and discussed in this section.
As shown in Fig. 25, two possible kinds of cation doping, namely,
cave doping and interlayer doping have been observed. Their
detailed doping mechanism was shown in Fig. 26. On the one
hand, the metal ions (Mn+ ) can be incorporated into the large caves
(the triangular pores) between the connected triazine structures
in the plane of g-C3 N4 (as shown in Fig. 26a), through the strong
coordination interactions between them and negatively charged
nitrogen atoms, thus achieving the so-called cave doping [297].
The previous studies revealed that the transition metal ions, such
as Fe3+ , Zn2+ , Mn3+ , Co3+ , Ni3+ and Cu2+ can be doped into the
large caves of g-C3 N4 [245,298303]. The DFT calculations demonstrated that the cave doping of Pt and Pd atoms could effectively
improve the carrier mobility, narrow the bandgap or optical gap,
and enhance the light absorption, which are favorable for photocatalytic reactions [304]. More interestingly, it was revealed that the
cave doping of alkali-metal ions such as Li+ , Na+ , and K+ will induce
the un-uniform spatial charge distribution in different intercalated
regions, increase the free carrier concentration, improve charge
transport and separation rate [106]. Recently, Zhu and coworkers demonstrated that the K+ doping could decrease the VB level

of g-C3 N4 , thus resulting in enhanced separation and immigration of photo-generated carriers under visible light [305]. More
recently, Dong and coworkers revealed that K atoms could achieve
an interlayer doping (as shown in Fig. 26b), instead of the cave
doping of Na atoms in g-C3 N4 [306]. It is believed that K atoms can
bridge the two adjacent g-C3 N4 layers, which lead to the narrowed
band gap, extended conjugated systems, and positive-shifted
valence band position, thus achieving the increased visible-light
harvesting, efcient charge separation, and strong oxidation capability, respectively. In contrary, despite of the increased in-planar
electron density and visible-light absorption, the cave doping of
Na atoms still exhibits high recombination rate of carriers in the
g-C3 N4 planes, thus resulting in the reduced photocatalytic performance [306]. This work might provide new insights into the deep
understanding on the metal doping of g-C3 N4 and the design of
electronically optimized layered photocatalysts for enhanced solar
energy conversion.
Apart from metal doping, the non-metal doping of g-C3 N4 has
been majorly realized through the chemically substituted doping.
As displayed in Fig. 16, almost all the non-metal doping, such as
S [118,182,307311], P [183,312316], B [114,317320], O [184],
C [185], and I [128,186], could narrow the bandgap of g-C3 N4 and
enhance its light harvesting capability. In general, the C self-doping
can substitute the bridging N atoms [185], whereas the O [184,321],
S [307,309,322] and I [128,186] doping could achieve the replacement of N atoms in the aromatic triazine rings (as shown in Fig. 27).
Interestingly, the doping of these different elements can promote
the delocalization of the -conjugated electrons, which is fundamentally important for improving the conductivity, mobility and
separation of photo-generated electrons, thus greatly enhancing
the photocatalytic performances of doped g-C3 N4 . In the contrary, the substituted doping of P [183,315,316,323326] and B
[327,328] atoms preferentially occur on the C atoms, thus leading to the formation of strong Lewis acid sites (P+ ) on the basic
surface (from amine or imine groups) of g-C3 N4 , due to the intrinsic polarization of PN bond and delocalization of one extra lone
electron in electron-rich P atom [324]. Most recently, Qiaos group
demonstrated that the P-doping of porous g-C3 N4 nanosheets can
drastically narrow the intrinsic band gap from 2.98 to 2.66 eV and
promote the photo-excitation of electrons from the VB of P-doped
g-C3 N4 , due to the formation of vacant midgap states below the
CB minimum of g-C3 N4 through the hybridization of C 2s2p, N
2s2p and P 3s3p, thus enhancing visible light absorption [326].
Meanwhile, it was also demonstrated that the (NH4 )2 HPO4 as phosphorus precursor could achieve the cave doping (in the interstitial
sites, as shown in Fig. 27). Furthermore, it is well known that S
atoms have been found to preferentially substitute N atoms with a
larger electronegativity (3.04), thus leading to the decreased VB/CB
levels and band gap [118,182,199,307,310,329]. Nevertheless, as

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Fig. 26. Two kinds of metal ion doping of g-C3 N4 framework: (a) cave doping, the incorporation of metal ions (Mn + ) through the coordination interactions, Color scheme:
C, red; N, yellow [27]; (b) interlayer doping (the interlayer bridging pattern for K) [306]. (For interpretation of the references to colour in this gure legend, the reader is
referred to the web version of this article.)

Fig. 27. Possible substituted sites of non-metal doping in the single layer of g-C3 N4 .

special cases, in situ sulfur and boron doping of g-C3 N4 has also
been found to replace the C and N atoms in the rings, respectively [182,330]. In addition, the F doping (NH4 F as a cheap uorine
source) can achieve the formation of the C F bonding in g-C3 N4
(as shown in Fig. 27), thus lowering the electronic band gaps [331].
However, it should be point out that excessive doping of nonmetal
and metal is found to be detrimental to enhance the photocatalysis,
because the more defects can also act as the recombination centers
of electronhole pairs. In future, the co-doping of different metals
and/or nonmetals, such as Fe/P [332] S/Co/O [333], S/P [334], P/O
[335], K/Na [336] and C/Fe [337] deserves more attention, due to
their positive synergetic effects on the visible-light absorption and
photocatalytic properties.
In addition, copolymerization at molecular level was also widely
employed to strongly enhance the photocatalytic activity of g-C3 N4 ,
via simultaneously modulating its band gap, electronic structures
and physical and chemical properties. Commonly, it is believed
that the copolymerization modication with structure-matching
aromatic compounds or organic additives could increase the
desired delocalization of -conjugated electrons and improve the
intrinsic drawbacks in g-C3 N4 , thus maximizing the photochemical activities [54,338341]. For example, Wang and co-workers
demonstrated that the tunable bandgaps of tri-striazine-based
g-C3 N4 ranging from 2.67 to 1.58 eV could be obtained (as
shown in Fig. 28a) through the copolymerization of dicyandiamide (monomer) and different amounts of barbituric acid (BA,
comonomer) [84]. More interestingly, 2D g-C3 N4 nanosheets fabricated by the one-pot condensation of urea and electron-rich

thiophene co-monomers could achieve the highest quantum efciency of 8.8% at 420 nm for H2 generation, (Fig. 28b) owing to
the narrowed band gap, improved electron migration and through
the formation of surface dyadic structures [129,342]. In contrary,
the molecular doping by an electron-decient pyromellitic dianhydride could thereby enhance the strong photooxidation capability
of g-C3 N4 , due to greatly decreased both the CB and VB positions [343]. To sum up, as a unique bottom-up way for tailoring
the bandgap of g-C3 N4 , the copolymerization approach provides
more opportunities for designing highly effective polymeric photocatalysts with desired electrical properties and band gap through
incorporating structure-matching organic moleculars, which also
provides insights into the mechanism of heterogeneous photocatalysis of organic semiconductors at molecular levels.

4.2. Defect control


It is widely accepted that a high degree of crystallinity is
advantageous for enhancing the photocatalytic redox reactions,
as compared to the negative roles of defects as chargerecombination sites [7]. For example, ionothermal synthesis
[102,103,105,108,344,345] thermal polymerization in ammonia
[346] and microwave-assisted heating synthesis [112,113] have
been broadly employed to achieve the highly crystalline g-C3 N4 for
efcient photocatalytic hydrogen evolution. It is believed that the
enhanced crystallinity of g-C3 N4 could improve the charge-carrier
mobility and separation, thus leading to signicantly improved
photoactivity. However, more recently, as an effective strategy,

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Fig. 28. (a) UVvis absoprtion spectra of g-C3 N4 and CNBx (arrow direction, x = 0.05, 0.1, 0.2, 0.5, 1, 2), where x refers to the weight ration of barbituric acid [84]. (b) H2
evolution over different g-C3 N4 copolymerized by urea and various monomers (3wt%Pt as co-catalyst) [129].

Fig. 29. (a) UVvis absorption spectra g-C3 N4 (GCN) and amorphous g-C3 N4 (ACN). Inset: Schematic of monolayer crystalline GCN and ACN; (b) The detailed band structures
of GCN and CAN, as well as the redox potentials of water splitting [348].

Fig. 30. (a) Lateral view and (b) vertical view for the interactions between water and a layer of defect g-C3 N4 sheet. Red, white, gray and white spheres represent O, H, C
and N atoms, respectively. (c) Spatial distribution functions of O and H atoms projected onto the defect g-C3 N4 sheet within the rst layer [353]. (For interpretation of the
references to colour in this gure legend, the reader is referred to the web version of this article.)

the creation of nitrogen vacancies [347] or amorphous structures


[348] in g-C3 N4 , has been extensively demonstrated to improve the
visible-light activity, owing to the efciently extended absorption
edge and promoted lifetime of charge carriers. For example, Liu and
co-workers demonstrated the high-temperature Ar-atmosphere
treatment of bulk g-C3 N4 at 620 C could disrupt the weak interactions of hydrogen bonds and van der Waals forces, and destroy
the long-range order in crystalline g-C3 N4 structures, thus fabricating the amorphous g-C3 N4 with the short-range order (as shown
in the inset of Fig. 29a) [348]. Such structure disorder changes in
amorphous g-C3 N4 could effectively narrow its bandgap from 2.7
to 1.9 eV, corresponding to an obvious red-shift of absorption edge

from 460 to 682 nm (as shown in Fig. 29a). The further valence
band XPS analysis reveals that the levels of VB and CB could be
reduced by 0.31 and 0.61 eV, respectively, without affecting the
thermodynamic requirements for O2 evolution and water reduction (as shown in Fig. 29b). These results could open up new ways
to develop visible light-driven amorphous or defective g-C3 N4 photocatalysts.
Apart from Ar-atmosphere heat treatment, the hightemperature treatment of pristine g-C3 N4 in a H2 , NH3 or
vacuum atmosphere could also create nitrogen or carbon vacancies in carbon nitrides, thus achieving the narrowed band gap
and improved photocatalytic performances [347,349351]. For

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example, a novel g-C3 N4 photocatalyst with N-vacancy structures and a bandgap of 2.03 eV could be fabricated by heating
the melon in a H2 atmosphere [347], which exhibits promising
photocatalytic activities towards generating OH radicals and
decomposing the organic pollutant Rhodamine B. It is believed
that the nitrogen-vacancy defects could greatly widen visible light
absorption range and suppress the unexpected fast recombination
of photo-excited carriers, thus achieving the improved photoactivity. Similarly, it was also demonstrated that the introduction of
hydrogenated defects in g-C3 N4 nanosheets could greatly enhance
the photocatalytic hydrogen evolution [349,352]. Furthermore, a
simple thermal treatment under an NH3 atmosphere can not only
develop highly porous g-C3 N4 nanosheets with plenary carbon
vacancies through etching their lattice carbon sites by the reactive
radicals from the NH3 decomposition [350,351], but also can
enhance the surface area, porosity and crystallinity of condensed
g-C3 N4 , due to the greatly reduced N defects in the -conjugated
network [346]. More interestingly, through employing both DFT
and molecular dynamics calculations, Wu et al. indicated that
the defect within g-C3 N4 played a key role in the adsorption
and dissociation of water, whereas, water does not dissociate on
the perfect g-C3 N4 sheet (as shown in Fig. 30) [353]. However,
it should be noted that the excessive nitrogen vacancies as the
recombination centers could be also harmful for the photocatalysis
[354]. To demonstrate this point, Osterloh and co-workers found
that surface structure defects in g-C3 N4 , with energy levels at
+0.97 V and 0.38 V (vs.NHE), limit visible light driven hydrogen
evolution and photovoltage [191]. More interestingly, it was also
demonstrated that the vacuum heat-treatment at 500 C could
obtain the highest photoactivity for H2 evolution due to the
increased content of the tri-s-triazine phase and suitable N defects
in the tri-s-triazine ring building blocks [355], which are similar
to the previous report about the vacuum-treated titanium dioxide
[356]. Consequently, the controlled defect concentration in g-C3 N4
is crucial for achieving the ideal photoactivity.
4.3. Pore texture tailoring
Another attractive design strategy is to tailor the porous structures/texture of g-C3 N4 materials, which can signicantly increase
their exposed surface area and accessible channels(porosity) and
active sites in g-C3 N4 , thus facilitating the molecular mass transfer/transport, charge migration and separation, surface reactions
and light harvesting [83]. All these advantageous features can
benet the enhancement of photocatalytic efciency. So far, a
variety of highly porous g-C3 N4 with diverse nanoarchitectures
and morphology have been widely fabricated through several
typical pathways, such as hard templating (nanocasting), soft
templating (self-assembly along the structure directing agents),
self-templating (supramolecular self-assembly) and template-free
methods [27,48,54,357], which have been thoroughly summarized
in Table 4. The detailed comparison and discussion between them
will be highlighted in this section.
As observed in Table 4, it is clear that the hard templating
(nanocasting) strategy is deemed to be one of the most simple and
effective methods to construct mesoporous g-C3 N4 photocatalysts
with superior high surface area (up to 517623 m2 /g) [69,229,360].
In theory, various kinds of macro/mesoporous materials with super
high surface area can be employed as hard templates to construct porous g-C3 N4 . To date, various kinds of hard templates
such as porous anodic Al2 O3 [358,359], CaCO3 [370], graphene
oxide nanosheets, [151] CMK-3 mesoporous carbon [69], mesoporous silica (nanospheres, [123,361,363] foams, [229] SBA-15,
[122,170,362] chiral silica, [365,366] silica KIT-6, [368] and KCC1 [369]) have been available in developing highly porous g-C3 N4 .
Absolutely, the mesoporous silica materials have been demon-

strated to be the most widely used hard templates. Unfortunately,


the trapped air and the weak-acid walls of mesopores in the silica
templates greatly prevent the inltration and fast mass diffusion
of basic organic precursor molecules into them, thus leading to the
incomplete utilization of their porous structures and the limited
enhancement in the surface area of porous g-C3 N4 [59]. Thus, to
maximize the roles of porous silica templates, Zhang et al. demonstrated that the combined strategy of dilute HCl pretreatment of
SBA-15 and sonication-vacuum insertion could increase the surface
area of mesoporous g-C3 N4 up to 517 m2 g1 , due to the improved
surface reactivity of the silica and removed trapped air [360]. However, the hazardous agents for removing the silica templates, such
as NH4 F or HF, are harmful for environment, g-C3 N4 itself or other
materials in a g-C3 N4 -based composite photocatalysts, restricting
the practical applications of hard-templating strategy in a large
scale. Thus, it is expected that more and more easy-removal or nonremovable hard templates, such as CaCO3 , Al2 O3 , Fe2 O3 and various
nanocarbons, should be further developed and applied in the fabricating the highly porous g-C3 N4 with different nanostructures
[69].
The greener soft-template route is also an interesting strategy to avoid various kinds of unfavorable factors aforementioned
for the hard-templating methods, which has also witnessed great
advances in developing porous g-C3 N4 micro-and nanostructures.
In general, the amphiphilic organic molecules are easy to form selfassembly micelles with different structures in solution, which can
function as soft templates (structure directing agents) to induce the
growth of precursors around them and further form expected composite structures [54,357]. Clearly, so far, various soft templates,
such as ionic liquids [114,373], Pluronic P123, [374,375] Triton X-100 [374,376,377], bubble [378381,383] and biomolecules
[279,382,384] have been widely utilized in the fabrication of porous
g-C3 N4 photocatalysts. For example, Zhang et al. demonstrated
that the mixture of 1-butyl-3-methylimidazolium tetrauoroborate (BmimBF4 , as a soft template) and dicyandiamide could
achieve the B/F-co-doped mesoporous g-C3 N4 with a surface area of
444 m2 g1 and a large total pore volume (0.32 m2 g1 ) [114]. Similarly, the nanoporous g-C3 N4 fabricated by using Pluronic P123
block polymers as a soft template, could exhibit a high surface area
of 299 m2 g1 [374]. However, the obvious disadvantages of ionic
liquids and polymers, such as the high cost, unexpected carbon
residue and insolubility in water, greatly limit their extensive practical applications in a large scale. At this regard, the use of bubbles
of water vapor as soft templates seems more promising in synthesis of porous g-C3 N4 , due to the absence of impurities and post
treatments [380,383]. Also, the interesting biomolecules as soft
templates are highly desirable in the future studies [279,382,384].
In addition, much attention has also been paid to the
supramolecular self-assembly and template-free methods. For the
supramolecular self-assembly strategies, it has been demonstrated
that the formation of hydrogen-bonded supramolecular assemblies (or complex) between melamine precursores and triazine
derivatives plays key roles in determining the different nanostructured morphologies of porous g-C3 N4 materials [385388]. For the
template-free route, the (hydro) solvothermal [328,394,397,398]
and freezing assistant assembly [395,396] methods have been
successfully exploited to fabricat porous g-C3 N4 materials. However, compared to the hard-templating methods, the surface area
of porous g-C3 N4 prepared by these two strategies is still much
smaller. More importantly, there are only limited precursors which
could form ordered and stable supramolecular aggregates in a solvent, based on noncovalent interactions (e.g. hydrogen bonding).
Accordingly, it is expected that these two appealing approaches
could be nely controlled and combined with other strategies, such
as an infrared heating process [399] or a simple reux method
[400], to design and fabricate highly efcient porous g-C3 N4 -based

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19

Table 4
Summarization of different fabrication methods for mesoporous g-C3 N4 .
Morphology

Templates

Precursor

Hard templating methods


Nanotubes
Nanorods
Ordered mesoporous
Mesoporous

Porous anodic Al2 O3 (AAO)


membranes
Ordered Mesoporous SBA-15
12-nm SiO2 particles

EDA, CTC
CA
CA
CA

SBA-15 pre-treated with 1 M HCl


Mesostructured cellular silica foams
Uniform-sized silica
nanospheres
SBA-15 nanorods

CA
EDA, CTC
CA

SBA-15
12-nm SiO2 particles
Monodisperse silica@ mesoporous
silica
Chiral mesoporous silica
Chiral silica
nanorods
7 nm colloidal silica particles

ATC
ATC
CA

2.78

CA
CA

2.75
2.7

Graphene oxide sheets


CMK-3 mesoporous carbon
Ordered mesoporous silica KIT-6
KCC-1 silica spheres
CaCO3
ZnCl2
MA sponge

MA
CA
CA
CA
DCDA
DCDA
Urea

Ionic liquids(BmimBF4 )
BmimBF4
BMIM-PF6
BmimDCN
Pluronic P123

DCDA
Urea
DCDA
DCDA
MA

Pluronic P123
Triton X-100
Triton X-100
Triton X-100
Bubble (urea)
Bubble (thiourea)
Bubble (water vapor)
Ammonium alginate or gelatin
Bubble (sublimed sulfur)
Bubble (sucrose)
Bubble (water)
Diatomite

DCDA
DCDA
MA, GA
MA sulfate
DCDA
DCDA
Urea
DCDA
MA
MA
urea
CA

Ordered mesoporous
Hierarchical mesostructures
Inverse opal
structures
Mesoporous
nanorods
Ordered mesoporous
Mesoporous
Hollow nanospheres
Helical rodlike
Porous nanorod
Mesoporous
sphere
Porous composite
g-C3 N4 @CMK-3 composite
Cubic mesoporous
Nanosheet-based nanospheres
Porous
Porous
Macroscopic 3D Porous monolith
Soft templating methods
Sponge-like mesopore
Porous nanosheets
Nanoporous
Worm-like
porous
Nanoporous
Nanoporous
Bimodal mesoporous
Nanoporous
Nanoporous
Porous
Sponge-like
Mesopore
Mesopore
Honeycomb-like
Diatom-structure

Template-free methods
Nanobelts
Porous
Porous
Hierarchical structure
Nanoporous
Nanosheets
Seaweed-like architecture
Monolayer mesoporous
Porous microspheres
Nanosheets
Nanorod-network superstructures

MA
MA hydrochloride
DCDA
MA
MA
urea
DCDA
DCDA
CAC/MA
Urea, Ph4 BNa
CAC/MA

Solvothermal in acetonitrile (180 C)

BJH pore
size (nm)

Pore
volume
(cm3 g1 )

5.3

0.34

8.3
3.4
4/43
20
70
3.9

0.41
0.49
0.9
0.79
1.7

5.3

0.34
0.77

2.7

2.86

[365] (2014)
[366] (2014)

224

[367] (2012)

0.08
0.76

26.6
623
208
160
38.6
46
78

[151] (2011)
[69] (2011)
[368] (2010)
[369] (2014)
[370] (2015)
[371] (2015)
[372] (2015)

25.0 23.4

0.32
0.40 0.51

444
73

5.6

0.179

81
90

0.128
0.284

299
116

17.6
3.0
3.6
3.8

0.09
0.49
0.4
0.4

2.472.57
3.7
18.2

0.321

2.49
50
13.2
2.65

0.355
0.68

3040

0.4
0.3

12.84

0.31

2.79

2.7

2.75
2.42
2.83
1.92

[360] (2013)
[229] (2010)
[361]
(2011)
[362] (2012)

56
52

3.8
3.8/1040

2.83
2.72
2.74
2.75
2.78

[358] (2009)
[359] (2011)
[122] (2009)
[123] (2009)

3.8/10.7

1.55

2.73
2.25

25
239
373
126
517
550
230
140
110200

Ref. (year)

[170] (2011)
[363] (2012)
[364] (2012)

2.89

2.72

BET surface
area
[m2 g1 ]

239
176
79

2.9

Urea

CAA/MA
MA/CAA
MA/CAA
CAA/MA
MA, urea, CAA
CA, MA, DPT
CAA, MA, BA
MA, TAP
CAA/MA

Freezing assistant assembly


Freezing assistant assembly/exfoliation
Solvothermal in acetonitrile (200 C)

2.9
2.74
2.7

CA

Self-templating (Supramolecular self-assembly) methods


Self-assembly
Hollow box
Self-assembly
Hollow spheres
Self-assembly
Spherical particles
Self-assembly
Hollow tube-like
Hollow to wormlike
Self-assembly
Self-assembly
Fiber-type/sheet-like
Self-assembly
Roll-like
Self-assembly
Crystalline
Self-assembly
Porous

Ball milling/hydrothermal method

Band gap
[eV]

15.8

0.50
0.15
1.41

<20
<20
16.2

0.62

90

[114] (2010)
[373] (2014)
[312] (2010)
[374] (2010)
[375] (2012)

50135
60
46.4
69.6
63
46
121
106
5

[374] (2010)
[374] (2010)
[376] (2011)
[377] (2014)
[378] (2014)
[379] (2013)
[380] (2012)
[279] (2013)
[381] (2015)
[382] (2015)
[383] (2015)
[384] (2013)

45
77
66
41
97.4
75 5
6070
119
77

[110] (2013)
[107] (2013)
[385] (2013)
[386] (2015)
[387] (2014)
[111] (2014)
[388] (2014)
[108] (2014)
[389] (2014)

69
201
35.6
30.9
288
130
331
8.5
144
30

[390] (2011)
[391] (2012)
[392] (2013)
[393] (2014)
[394] (2015)
[153] (2013)
[395] (2015)
[396] (2016)
[397] (2015)
[328] (2013)
[398] (2012)

BmimBF4 : 1-butyl-3methylimidazolium tetrauoroborate; BMIM-PF6: 1-butyl3-methylimidazolium hexauorophosphate; BmimDCN Ph4 BNa: sodium tetraphenylboron;
CA: cyanamide; MA: melamine; DCDA: Dicyandiamide; CAA: cyanuric acid; CAC: Cyanuric chloride; DPT: 2,4-diamino-6-phenyl-1,3,5-triazine; BA: barbituric acid; ATC:
ammonium thiocyanate; EDA: ethylenediamine; CTC: carbon tetrachloride; GA: glutaraldehyde, TAP: 2,4,6-triaminopyrimidine.

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semiconductors with high surface area and unique nanostructures in a low-temperature solution in future research [54]. In
addition, it is also expected that the two strategies of in situ
template-sacricial dissolution [401] and chemically induced selftransformation [217,402408] could be applied in developing
highly porous g-C3 N4 -based semiconductors.
4.4. Dimensionality tuning
Generally, compared with the bulk counterparts, nanostructured g-C3 N4 semiconductors with unique dimensions and
congurations could exhibit several obvious advantages for solar
photocatalysis, such as the higher surface area, shorter charge
migration length, higher solubility and tunable electronic structure [37]. Detailedly speaking, the charge carriers generated in
the ultrathin g-C3 N4 nanosheets can readily reach their surface
for redox reactions through the very short paths, as compared
to traditional 3D bulk g-C3 N4 semiconductors, thus achieving
the rapid charge separation. More importantly, through controlling the layer number without changing the atomic structure,
the energy band structure of g-C3 N4 could be effectively tailored due to the quantum connement effects, thus leading to
improved activity and selectivity for various reactions, such as CO2
reduction [409] and O2 reduction [410]. In addition, the nanostructured g-C3 N4 with different dimensions also exhibited signicantly
enhanced opened-up surface areas and highly exposed active
sites, thereby greatly facilitating the photocatalytic enhancements.
All these advanced features endow the nanostructured g-C3 N4
with attractive structure-dependent, morphology-dependent and
thickness-dependent applications ranging from photocatalysis to
other emerging elds. Thus, as a simple way, tuning physical
dimensions of g-C3 N4 has become a popular strategy to manipulate the optical, electrical, and redox properties, thus achieving the
desired catalytic activity, selectivity, and long-term stability. So far,
nanostructured g-C3 N4 with various different dimensionality, such
as 0D quantum dots [411414], 1D nanowires/nanorods/nanotubes
[138,277,359,395,400], 2D nanosheets [100,415,416], 3D hierarchical structures [393,417419] have been widely exploited and
applied in the photocatalysis [55]. Among them, the 2D ultrathin
g-C3 N4 nanosheets have proven to be more promising for various
photocatalytic applications [27,52,56], whose fabrication strategies
will be highlighted in this section.
Generally, the free-standing ultrathin g-C3 N4 nanosheets could
be obtained via two distinct synthetic strategies, including the
top-down exfoliation of layered bulk g-C3 N4 materials and bottomup assembly of precursors (molecular building blocks) in a 2D
manner [52,56]. Typically, these two fabrication strategies can
be further classied into ve detailed categories: ultrasonicationassisted liquid exfoliation, chemical exfoliation, thermal oxidation
etching, combined and other approaches. In order to facilitate
further comparison, various different fabrication methods for gC3 N4 nanosheets have been thoroughly summarized in Table 5. As
observed in Table 5, it is clear that the 2D single-layer and few-layer
g-C3 N4 nanosheets could exhibit much higher surface areas in the
range from 50 to 384 m2 g1 , which are several times larger than
that of bulk layered g-C3 N4 (10 m2 g1 ), thus signicantly favoring
the photocatalytic enhancement.
Inspired by the formation of graphene/metal dichalcogenide/double hydroxide nanosheets by liquid exfoliation of
layered bulk counterparts [463469], it is highly expected that the
mono- or few-layer C3 N4 nanosheets could be obtained through
a simple liquid exfoliation of bulk layered g-C3 N4 by sonication.
Clearly, the well matched surface energy between a liquid solvent
and g-C3 N4 (115 mJ m2 ) could effectively reduce their enthalpy of
mixing, thus leading to the enhanced exfoliation efciency of bulk
g-C3 N4 into 2D nanosheets [426,465]. Thus, the ultrasonication

treatments in various solvents with proper surface energy, such


as water (102 mJ m2 ), methanol, ethanol, N-methyl-pyrrolidone
(NMP), 1-isopropanol(IPA), dimethyl formamide(DMF), acetone,
acetonitrile, 1,4-dioxane and their mixtures, have been applied in
overcoming the weak van der Waals forces between the two adjacent g-C3 N4 layers and successfully exfoliating the bulk layered
g-C3 N4 into 2D ultrathin nanosheets [100,103,178,416,425,426].
For example, Xie and coworkers successfully prepared the ultrathin
g-C3 N4 nanosheets (0.15 mg/mL) with a size distribution ranging from 70 to 160 nm and a height of 2.5 nm (about 7 layers)
by a green liquid exfoliation route from bulk g-C3 N4 in water
for the rst time (as shown in Fig. 31a and b) [100]. To further
enhance the dispersion concentration of exfoliated mono-layer or
few-layer g-C3 N4 nanosheets, the better solvent effects of organic
and mixed solvents have been utilized to exfoliate the bulk C3 N4
materials [424,429]. For example, the exfoliation of commercial
g-C3 N4 in the mixed solution (ethanolamine, 1,3-butanediol and
3-pyridinemethanol) could obtain the 7-layer g-C3 N4 nanosheets
with a concentration of 1 mg/mL [429]. In another example, the
single layer of g-C3 N4 nanosheets with a concentration of 3 mg/mL
have been achieved through the effective exfoliation in the mixed
water/organic solvents [424]. However, some typical problems,
including the use of organic solvents and additives, long ultrasonication exfoliation time and low yield, still need to be further
overcome. Thus, the liquid ammonia-assisted lithiation and the
intercalation of LiCl ions have been exploited to achieve the largescale exfoliation of bulk g-C3 N4 materials [430,431]. Especailly, the
8-layer-thick O-doped g-C3 N4 nanosheets could be fabricated by
this liquid ammonia-assisted lithiation method in a large scale
(10 g) and high yield (85%), under mild conditions [430]. More
fortunately, it was demonstrated that the chemical exfoliation in
acid or alkaline solution could not only obtain amphoteric singlelayer g-C3 N4 nanosheets with the negatively charged carboxyl and
positively charged NH2 /NH3 + groups, but also efciently reduce
the ultrasonication-treatment time from more than 10 h to 2 h
[82,178,432,470]. For example, Xu et al. successfully obtained single layer of g-C3 N4 nanosheets with a thickness of 0.4 nm by
means of the rapid exothermic effect of the intercalated concentrated H2 SO4 (98%) dissolving in deionized water [178]. Following
this report, Tong et al. developed an interesting high-throughput
method to rapidly fabricate g-C3 N4 nanosheets through combining the oxidation, protonation and heating effects of concentrated
H2 SO4 [432]. The g-C3 N4 nanosheets with a thickness of 2.5 nm
and different degree of exfoliation could be easily achieved though
directly adding controlled amount of H2 O into a bulk g-C3 N4
suspension using the concentrated H2 SO4 as solvent. This facile
acid-exfoliation method with low cost and controlled exfoliation
degree would open up new opportunities for the large-scale fabrication and extensive application of g-C3 N4 nanosheets.
Although bulk g-C3 N4 could be also easily thermally exfoliated
into 2 nm-thickness nanosheets (around 67 layers) through the
direct oxidation etching [415], the poor yield (<6%) and signicant
interface defects, thus leading to the signicantly reduced photoability and photoactivity. Motivated by the successful thermal
exfoliation of the NH4 Cl-intercalation g-C3 N4 materials [449], Wu
and coworkers recently developed a facile one-step dicyandiamideblowing method with NH4 Cl as the gas template to achieve the
scalable fabrication of high quality 2D g-C3 N4 nanosheets [443].
As shown in Fig. 32, it is believed that the gases (NH3 and
HCl) released from NH4 Cl during heating directly achieved the
fast exfoliation of bulk g-C3 N4 into the crinkly 8-layer g-C3 N4
nanosheets (with a thickness of 3.1 nm and a high band gap of
2.83 eV). Other methods such as thermal exfoliation of C3 N4 -based
intercalation compound [449], microwave heating [462] and ball
milling [461] have also been successfully applied in obtaining 2D
ultrathin C3 N4 nanosheets. More interestingly, the perfect com-

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Table 5
Summarization of different fabrication methods for g-C3 N4 nanosheets.
Bulk g-C3 N4

Solvents, bulk powder/solvent


(mg/ml), time (h)

Ultrasonication-assisted liquid exfoliation


Water, 100/100, 16 h
MA (P, 600 C)
Poly(triazine imide) (I)
Water, 2/1, 15 h
Water, 200/200, 24 h
CA (P, 530 C)
Water, 50/50, 10 h
MA (P, 600 C)
Water, 50/50, 10 h
MA (P, 600 C)

Water, 100/200, 16 h
MA (P, 600 C)

MA (P, 550 C)
Water, 50/50, 2 h
Water/organic solvents, 500/150, 10 h
MA (P, 550 C)
Isopropanol, 30/10, 10 h
Commercial g-C3 N4
(Carbodeon Ltd)
CA (P, 550 C)
Ethanol, 50/50, 2 h
1,3-butanediol, 60/25, 24 h
DCDA (P, 600 C)

MA (P, 550 C)
30 wt% isopropanol + water, 4/1, 10 h

Water, 100/200, 16 h
MA (P, 600 C)
DMF, 50/200, 2h(80 C)+ melamine
DCDA (P, 520 C)
Ethanolamine/1,3-butanediol/3Commercial g-C3 N4
(Carbodeon Ltd)
pyridinemethanol,30/10,4h
Chemical exfoliation
MA (P, 550 C)
MA + LiCl(P, 380 + 550 C)
DCDA (P, 550 C)
MA (P, 550 C)
DCDA (P, 550 C)
DCDA (P, 550 C)
MA (P, 550 C)
MA (P, 550 C)
MA (P, 520 C)
MA (P, 600 C)
Thermal oxidation etching
DCDA (P, 550 C)
DCDA(P, 550 C)
Urea (P, 550 C)
MA (P, 550 C)
MA (P, 550 C)
MA (P, 520 + 540 C)
MA (P, 500 + 520 C)
MA (P, 500 + 550 C)
MA (P, 600 C)
DCDA (P, 520 C)
Commercial g-C3 N4
(Carbodeon Ltd)
DCDA(P, 550 C)
Mixed DCDA/NH4 Cl
Mixed DCDA/NH4 Cl
Mixed MA/KCl
Mixed MA/KBH4
Guanidinium cyanurate
Guanidinium chloride
DCDA (P, 600 C)
Combined approaches
MA (P, 520 C)
MA (P, 500 + 530 C)
MA (P, 500 + 530 C)
MA (P, 520 C)
MA (P, 550 C)
MA (P, 520 C)
DCDA (P, 550 C)
DCDA/2-aminobenzonitrile (P,
550 C)
Urea (P, 600 C)

0.15/
0.2/

2.70/

/14.5
/14.5
/8.6

2.5/7
12/36
1.8/56
1.2/4
1.0/3

2.6/

3/

1.2/<5
0.38/1
2/ < 9

2.79/59.4
2.65/384

0.35/

23/58
0.92.1/36
2/6

2.73/112.5
2.79/32.54
2.70/

23/69
7

2.75/116.76

/8.6
1/

[100] (2013)
[103] (2014)
[410] (2013)
[299,420](2013)
[421] (2013)
[422] (2013)
[423] (2014)
[424] (2015)
[416] (2013)
[425] (2014)
[426] (2014)
[427] (2014)
[422] (2013)
[428] (2015)
[429] (2015)

/85%

2.5/8
23/69

2.78/22.5
2.82/186

[430] (2014)
[431] (2016)

/30%

0.4/1

2.92/205.8

[178] (2013)

/70%
300/
/2530%

2.5
/1
24/610

2.93/86.29
3.28/
2.75/305
/109.3
/65

[432] (2015)
[180] (2015)
[82] (2014)
[433] (2014)
[164] (2013)

/2530%

9.0/30

3.42/
2.7/179.5

[82] (2014)
[434] (2015)

Air, 500 C, 2 h
Air, 500 C, 2 h
Air, 550 C, 2 h
Air, 500 C, 2 h
Air, 500 C, 2 h
Air, 540 C, 2 h
Air, 520 C, 4 h
Air, 500 C, 2 h
Air, 500 C, 4 h
Air, 400 C, 4 h
H2 , 400 C, 4 h

/<6%
/<6%
/8.0

1.622.62/47
1.622.62/47
16/

2.97/306
2.97306
2.86/151
3.06/165.66
2.91/122.6
2.93/210
2.82/153.32
2.97/150.1

[415] (2012)
[409] (2014)
[435] (2015)
[436] (2014)
[326] (2015)
[437] (2015)
[438] (2016)
[439] (2014)
[440] (2015)
[441] (2013)
[442] (2015)

58/1020
/0.35%
2.7/8
1.9/6
0.9/3
2/6

NH3 , 510 C, 1 h
Air, 550 C, 2 h
Air, 550 C, 4 h
Air, 550 C, 4 h
Air, 550 C, 4 h
Air, 550 C, 4 h
Air, 600 C, 4 h
Air, 350 C, 2 h (NH4 Cl intercalation, N2 )

20/50
3.1/8
1.0/3
1.56.3
1.5/4
0.61.5/13

(Air, 550 C, 3 h)+ (isopropanol, 10/100, 8 h)


(Air, 550 C, 3 h)+ (methanol, 100/100, 4 h)
(Air, 550 C, 200 min)+ (methanol, 100/100, 4 h)
(Air, 550 C, 3 h)+ (isopropanol, 8 h)
(Air, 550 C)+ (H2 SO4 + HNO3 , 100/40, 5 h)
(Air, 550 C, 3 h)+ (0.5 M HCl, 20/200, 8 h)
(H2 SO4 (98 wt%), 2000/50, 2 h) + (water, 1 h)
(5 M HNO3 , 400/80, 20 h/under reux)+ (water, 4 h)

0.5/1
0.40.5/1
0.81.2/23
0.5/1

MA (P, 550 C)
Other approaches
MA (P, 550 C)
MA and carbon bre

Ball milling method


Microwave heating approach

MA (P, 550 C)

Band gap (eV) /surface Ref. (year)


area (m2 g1 )

Liquid ammonia-assisted lithiation


The intercalation of LiCl ions and the liquid
exfoliation in water
H2 SO4 (98 wt%) treatment for 8 h, then rapid
exfoliation
H2 SO4 (98 wt%), 1000/15, 15 min
H2 SO4 (98 wt%)
HCl treatment for 1 h, then exfoliation for 2 h
6 M HCl, 320/80, hydrothermal at 110 C for 5 h
0.1 M NaOH, 1000/90, hydrothermal at 150 C for
18 h
HCl treatment for 1 h, then exfoliation for 2 h
HNO3 (63 wt%) treatment for
8 h, then sonicated exfoliation

(H2 SO4 + HNO3 , 1000/200, 4 h)+


(water, 30/30, 2 h)
(75 wt% H2 SO4 , 300/30, 2 h 130 C)
+ (water + 300/200,2 h)
(H2 SO4 (98 wt%), 1000/10, 8 h) + (N2 , 550 C, 2 h)

Thickess (nm) /Layer


Concentration
(mg/mL)/Yield (%) numbers

23/69

0.6/1
510/1520
0.64/210

2.89/
/260
2.95/196
2.83/52.9
2.77/77.7
2.71/
2.87/133.8
2.44/109.9
2.85/30.1

3.03/
3.0/380
2.95/109.30
3.0/140
2.89/

/10.5

[350] (2015)
[443] (2014)
[444] (2015)
[445] (2014)
[446] (2014)
[447] (2015)
[448] (2014)
[449] (2014)
[450] (2014)
[451] (2014)
[452] (2015)
[453] (2014)
[454] (2014)
[455] (2015)
[456] (2015)
[457] (2016)
[458] (2016)

2.5/7

2.88/80

[459] (2015)

0.81.4/34

2.79/54.3

[460] (2016)

/12
1.6/5

2.98/
2.88/239

[461] (2015)
[462] (2016)

P, pyrolysis (or thermal polycondensation); DMF, dimethylformamide.

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Fig. 31. (a) Schematic illustration for the synthesis process of ultrathin g-C3 N4 nanosheets via liquid exfoliation. (b) AFM image of the synthetic g-C3 N4 nanosheets. (d) The
corresponding height image of two random nanosheets [100].

4.5. Surface sensitization

Fig. 32. Schematic illustration for fabricting the ultrathin nanosheets of g-C3 N4
through a dicyandiamide-blowing method [443].

bination of liquid, chemical exfoliation and thermal oxidation


etching could fully explore their potentials and achieve the lowcost, simple, fast and scalable synthesis of 2D g-C3 N4 nanosheets
[450,451,453,455,457,460], which deserves more attention in the
near future.
In addition to developing new fabrication methods of g-C3 N4
nanosheets, more efforts should be also devote to narrowing their
larger band gaps (0.10.2 eV higher than that of bulk g-C3 N4 ) and
promoting the fast utilization of photo-generated charge carriers
migrated to the surface of g-C3 N4 nanosheets. As effective strategies, doping [84,118,128,328,471], introducing nitrogen vacancies
[347,472], sensitization [473], copolymerization [130,474,475] and
hybridization with other semiconductors or co-catalysts could be
employed to further achieve the 600 nm or near-infrared (NIR) photocatalysis of g-C3 N4 nanosheets in aqueous solution [52,476478].

In general, there are ve typical strategies to increase the visiblelight absorbance of wide band gap semiconductors: band-gap
engineering (impurity doping and solid solution), defect control, surface plasmon resonance (SPR) effect, sensitization by dye
and quantum dot [16]. Although the aforementioned two strategies of band-gap engineering and defect control can partially
extend their visible-light absorption, the moderate band gaps
(2.7 eV) of g-C3 N4 -based semiconductors are still the main bottlenecks affecting the highly effective generation of photo-generated
charge carriers, which thereby play the crucial roles in determining the visible-light photocatalytic performances of g-C3 N4 -based
semiconductors. Thus, other three strategies, including loading
plasmonic metals, sensitization by quantum dots (QDs) and organic
dyes (the corresponding mechanisms shown in Fig. 33), have been
also widely applied in enhancing the visible-light absorbance of gC3 N4 -based semiconductors, which will be thoroughly discussed
in this section.
Firstly, the famous SPR effects of noble metals, such as
Au [77,200,479482] and Ag [433,455,479,483492], have been
widely employed to improve the visible-light absorbance and
charge separation of g-C3 N4 . In general, it is well accepted that
the deposited plasmonic metals could function as electron sink,
reduction co-catalyst and photosensitizers to enhance the visiblelight absorption of a given semiconductor [493]. For example, Bai
et al. fabricated the coreshell nanostructured Ag@C3 N4 photocatalysts through the simple methanol-reux treatment of g-C3 N4
nanosheets deposited by Ag nanoparticles (as shown in Fig. 34)
[488]. The combination of LSPR effect of Ag nanoparticles and their
hybrid effect with C3 N4 could achieve 1.8- and 30-time enhancements in the photocatalytic MB degradation and H2 evolution,
respectively. In another example, Wei et al. constructed the type-II
2D-1D C3 N4 /TiO2 hybrid nanobers and further decorated plasmonic noble metal nanoparticles (Au, Ag, or Pt) with sizes from 5

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Fig. 33. Mechanisms for g-C3 N4 photocatalysts sensitized by (a) plasmonic metals, (b) quantum dots (QDs), (c) organic dyes.

Fig. 34. Synthetic route and charge-separation mechanism for C3 N4 and coreshell
nanostructured Ag@C3 N4 photocatalysts under light irradiation [488].

to 10 nm on them [479]. The resulting SPR sensitized heterostructures could achieve highly efcient photocatalytic H2 evolution
due to the simultaneous implementation of improved light absorption, charge separation and utilization. In future, it is expected that
the plasmonic alloys [494,495], Cu [496498] and Bi [499501]
nanoparticles could be deposited onto g-C3 N4 to boost their visiblelight photocatalytic activity.
Secondly, the quantum dots modied g-C3 N4 photocatalytic
systems are still very interesting and promising [502505]. For
example, Ge et al. rst demonstrated that the deposition of 30 wt%
CdS QDs onto the bulk g-C3 N4 could achieve a 9-fold enhancement
in the visible-light photocatalytic H2 -evolution activity, due to the
increased the absorbance of visible light and promoted charge separation [502]. Since then, CdS QDs have been widely used to improve
the visible-light activity of bulk g-C3 N4 for various kinds of applications [284,405,502,503,506508]. In future, it is expected that
more efcient CdS/g-C3 N4 composite photocatalysts with earthabundant co-catalysts should be further exploited.
Thirdly, various kinds of low-cost organic dyes, such as magnesium phthalocyanine (MgPc) [509], zinc phthalocyanine [510515],
Xanthene [516], Erythrosin B (ErB) [473,517] and Eosin Y (EY) [518],
have been readily coupled with different nanostructured g-C3 N4
to fabricate the highly efcient organic semiconductor heterojunctions. For example, Domen and his coworkers deposited an organic
MgPc dye (with a band gap of 1.8 eV) on the Pt/mpg-C3 N4 composite semiconductors and achieve the enhanced photocatalytic
H2 evolution under long-wavelength irradiation (>600 nm) [509].
The results indicated that the monolayer dye could achieve the
highest photocatalytic H2 -evolution performance due to promoted

charge generation, transfer and utilization, whereas excess thickness of the dye layer will cover the co-catalyst sites, thus reducing
the photocatalytic activity [509]. Similarly, Lu and coworkers
successfully demonstrated that the sensitization of mesoporous
g-C3 N4 with a EY dye could achieve an H2 -evolution AQE of
19.4% under 550 nm irradiation [519]. It is suggested that the
high surface area and nanoporous structure of mpg-C3 N4 are
greatly favorable for deposition of EY molecules on its surface,
thus promoting the signicantly increased and extended light
harvesting in the visible-light response region and further improving H2 -evolution activity. More surprisingly, Xu and coworkers
demonstrated that the deposition of ErB dye onto Pt/g-C3 N4 sample exhibited a remarkably enhanced H2 evolution rate (652.5 or
162.5 mol h1 ) from an aqueous solution of TEOA under visible
light irradiation ( > 420 nm or > 550 nm), with an AQY of 33.4%
at 460 nm [473]. The resulting ternary Pt/g-C3 N4 /ErB photocatalyst also showed the stability and good recyclability, remaining
90% of the activity after 5 runs [473]. Most recently, it has been
demonstrated that the promising earth-abundant Co(OH)2 and
MoS2 could be utilized as co-catalysts to boost the photocatlytic H2 evolution activity over these dye-sensitized g-C3 N4 photocatalysts
[517,520,521]. More interestingly, the g-C3 N4 -based photocatalytic
systems co-sensitized by two organic dyes or inorganic photosensitizers (plasmonic metals and QDs) are also highly desirable in
future studies [510,512,521,522]. However, the apparent quantum
effciency and stabilities of these systems are still needed to be further enhanced.

4.6. Heterojunction construction


Enhancing photocatalytic activity of g-C3 N4 -based semiconductors could be also achieved through constructing semiconductor
heterojunctions, which could induce the band bending and the
formation of internal electrical eld, thus signicantly boosting
the efcient spatial charge separation [7]. In general, according
to the semiconductors energy bands and Femi levels of metal
co-catalysts, semiconductor heterojunctions can be divided into
four types: Schottky junction (Fig. 35A), Type I (Fig. 35B), Type
II (Fig. 35C) and Type III (Fig. 35D) heterojunctions. Clearly, only
Schottky junction and Type II heterojunctions can signicantly
promote the fast spatial separation of electrons and holes, thus
retarding their recombination and prolonging their lifetime. Thus,
for photocatalysis, the construction of Schottky junction and Type
II alignment should be highly desired. The Schottky junction will
be discussed in the next section. Here, we will focus on the Type
II g-C3 N4 -based heterojunctions. As observed the CB and VB levels of different semiconductors in Table 1 and Fig. 16, it is easily
found that several commonly used semiconductors, such as TiO2
[523], Cu2 O [524526], ZnO [291,527537], WO3 [286,538544],
BiVO4 [545551], (BiO)2 CO3 [552], Ag3 PO4 [553560], CdS
[197,284,405,502,503,506,508,561566], BiOX [567575], Bi2 WO6
[552,576583], Fe2 O3 [115,289,584587] and different types of gC3 N4 [121,588] can be combined with g-C3 N4 to construct the Type

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Fig. 35. Spatial charge-separation mechanisms for four different types of semiconductor heterojunctions: (A) Schottky junction, (B) Type I, (C) Type II, and (D) Type III
heterojunctions.

II heterojunctions and achieve the efcient charge separation. Here,


the CdS/g-C3 N4 and the g-C3 N4 isotype heterojunctions will be
discussed.
Besides the above mentioned systems of CdS quantum
dots/g-C3 N4 [502,503,561], various kinds of other nanostructured combinations, such as core/shell CdS@g-C3 N4 Nanowires
[284,562], g-C3 N4 /Au/CdS Z-scheme [589,590], CdS nanoparticles/2D g-C3 N4 nanosheets [563] and CdS nanorods/g-C3 N4
nanosheets [197,562,591,592] have been also successfully constructed to obtain the highly efcient and stable composite
photocatalysts. Among them, the core/shell heterojunctions seem
to be more promising, due to the suppressed CdS photocorrosion
and the optimized intimate interface contact. For example, Zhang
et al. demonstrated that the as-constructed novel CdS/2 wt% gC3 N4 core/shell nanowires could achieve an optimal photocatalytic
activity of up to 4152 mol h1 g1 [562]. It is believed that the
well-matched Type II g-C3 N4 /CdS heterojunctions could achieve
the positive synergic effect of accelerating the separation of charge
carriers and inhibiting the CdS corrosion (as shown in Fig. 36a), thus
greatly enhancing the photocatalytic activity and photostability
[562]. Interestingly, based on the slight difference in their electronic band structures (Fig. 36b), Wang and coworkers et al. rstly
demonstrated that the as-prepared Type II isotype heterojunctions
of g-C3 N4 /S-mediated g-C3 N4 (S-g-C3 N4 ) exhibited the matched
band gaps and efciently promoted charge separation of the band
offsets (Fig. 36b), thus signicantly enhancing photocatalytic activity for H2 evolution [121]. The isotype heterostructure is similar to
that of phase junction in the formation mechanism, which provides
new opportunities to construct buried layered junctions in the
various copolymerized g-C3 N4 -based composites with improved
charge photon-excitation and charge separation [54]. Similarly,
Dong and coworkers in situ constructed a novel Type II layered
g-C3 N4 /g-C3 N4 metal-free isotype heterojunction with enhanced
photocatalytic activity for the removal of NO in air [588]. The results
further conrmed the key roles of the Type II isotype heterojunction in achieving the efcient charge separation and transfer across
the heterojunction interface as well as prolonged lifetime of charge
carriers.
As observed in Figs. 35 b and 36, for the favorable Type II heterojunction systems, the photocatalytic redox reactions mainly
occur on the surface of semiconductor with lower CB and VB
edges, implying the weaker reduction and oxidation ability (driving
forces) in this kind of heterojunction-type photocatalytic system.
In contrary, as observed in Fig. 37, for the all-solid-state Z-scheme
photocatalytic system with the Ohmic-contact interfaces, their
photocatalytic activities are majorly dependent on the surface
properties of semiconductor with higher CB and VB edges, thus
leading to the strong redox ability and enhanced photocatalysis [593]. In nature, photosynthesis of plants generally proceeds
according to the so-called Z-scheme photocatalytic process, in

which two isolated reactions of water oxidation and CO2 reduction


are linked together through the redox mediators [593]. Mimicking
the natural photosynthesis process, the articial Z-scheme semiconductor heterojunctions have been successfully proposed and
constructed by combining two different semiconductors through
liquid-state or all-solid-state mediators. Each semiconductor in
the Z-scheme is only responsible for one (oxidation or reduction) reaction, thus achieving the extremely extended visible-light
absorption, strengthened redox ability, improved photostability,
charge-separation and photocatalytic efciency [594,595]. In this
regard, the all-solid-state g-C3 N4 -based Z-scheme photocatalytic
systems seem to exhibit many advantages and great potential
in practical applications in photocatalytic elds. Commonly, the
articial heterogeneous all-solid-state g-C3 N4 -based Z-scheme
photocatalytic systems could overcome the weak oxidation ability
and decrease the reduction capacity of single-g-C3 N4 and g-C3 N4 based heterojunctions, respectively, and simultaneously fulll a
wide absorption range, long-term stability, high charge-separation
efciency and strong redox ability [523,596,597].
Typically, two kinds of all-solid-state g-C3 N4 -based Z-scheme
photocatalytic systems with and without mediators are displayed
in Fig. 37a and b, respectively. For the rational design of these
two kinds of all-solid-state g-C3 N4 -based Z-scheme photocatalytic
systems, the achievement of the intimate Ohmic contact should
be the most important point, which could be obtained through
introducing the conductors, such as conductive carbon and metals, or fabricating the perfect interfacial contact. For example, Yu
and coworkers, for the rst time, constructed a direct g-C3 N4 TiO2
Z-scheme photocatalyst without an electron mediator by a facile
calcination route, which could achieve the intimate interfacial
contact [523]. The results showed that the as-prepared Z-scheme
photocatalysts was highly dependent on the g-C3 N4 content. Ideally, the surface of the TiO2 nanoparticles should be partially
covered by the g-C3 N4 nanoparticles, which are favorable for the
formation of a g-C3 N4 -TiO2 Z-scheme photocatalytic system (see
Fig. 38a and b). In contrary, the excessively high contents of gC3 N4 can not only lead to the complete cover of TiO2 surface,
which could decrease the charge carrier excitation of TiO2 , but also
increase the recombination rate of photo-generated electrons and
holes on g-C3 N4 (see Fig. 38c). Similar Z-scheme systems between
g-C3 N4 and TiO2 have also been observed in other reports [598,599].
Some other direct g-C3 N4 -based Z-scheme photocatalysts, such as
Bi2 O3 /g-C3 N4 [600], ZnO/g-C3 N4 [601,602], BiVO4 /g-C3 N4 [603],
g-C3 N4 /Bi2 MoO6 [604], WO3 /g-C3 N4 [605,606], g-C3 N4 /Ag3 PO4
[607609], BiOCl-g-C3 N4 [610], Bi2 WO6 /g-C3 N4 [505] have also
been available. Additionally, some typical electron mediators,
such as nanocarbon [611], Au [590,612], RGO [613] and Bi [614]
could be used to construct the indirect g-C3 N4 -based Z-scheme
photocatalysts. In future, improvements in the morphology of
semiconductors and interfacial coupling should be deeply and con-

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Fig. 36. Schematic illustration of spatial charge separation in CdS/g-C3 N4 (a) and g-C3 N4 /S-g-C3 N4 (b).

Fig. 37. Schematic illustration of spatial charge separation in the all-solid-state g-C3 N4 -based Z-scheme photocatalytic systems with (a) and without (b) mediators.

Fig. 38. Schematic illustration for the charge transfer and separation in g-C3 N4 -TiO2 Z-scheme photocatalysts under UV light irradiation [523].

tinually investigated to search for highly effective g-C3 N4 -based


Z-scheme photocatalysts for practical applications [598,615618].
More importantly, the direct or indirect experimental evidence
for supporting the proposed Z-scheme charge-transfer mechanism
should be provided as far as possible. In fact, the technologies such

as radicals ( O2 and OH) trapping experiments, metal deposition


and double-beam photoacoustic (DB-PA) spectroscopy have been
employed to reveal the real Z-scheme charge-transfer mechanism
[523,534,601,608,619,620].

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estingly, the layered triple-nanojunctions in the ternary g-C3 N4


nanosheets/N-doped graphene/MoS2 have also been successfully
fabricated, which has been shown to signicantly improve the photocatalytic activity of MB oxidation and Cr(VI) reduction through
the synergistic effects of multiple 2D-2D coupling interfaces [650].
These results highlighted that the unique 2D2D layered nanojunctions with larger contact area are more promising for the fast
separation of photo-excited charge carriers across the interfaces
with respect to the 0D2D and 1D2D coupling systems. More
interestingly, the coupling of g-C3 N4 nanosheets and semiconductor nanosheets with exposed facets seems to be more promising
in various kinds of photocatalytic applications, due to the diversied synergy effects [418,427,559,572,641,651656]. In future, it
is expected that the 2D2D interface coupling performances could
be further enhanced through improving the tightness of interfaces
and introducing the interfacial mediator [476,638].
Fig. 39. Schematic illustration of 2D layered composites in comparison with other
kinds of composites [476].

In addition, it should be also noted that the interfacial contact/coupling performances could be further improved by several
strategies, such as, increasing the contact areas, improving the
tightness of interfaces [621624] and introducing the highlyconductive interfacial mediator [625627]. Clearly, larger contact
area can provide sufcient charge transfer and trapping channels for achieving their fast separation. As compared with other
types of composite pohotocatalysts with 1D (i.e. 0D/1D and
1D/1D) or 2D (i.e. 0D/2D and 1D/2D) contact interfaces, the
unique 2D2D layered nano-junctions possess the much larger
contact surface between the two adjacent sheets (as shown in
Fig. 39), thus favoring more efcient interfacial charge separation and photo-activity enhancement [476]. More fortunately,
g-C3 N4 itself possesses a unique 2D layered structure, which holds
great promise for potential applications in constructing 2D layered
composite photocatalysts. In 2011, Xiang et al. rst constructed
graphene/g-C3 N4 composite photocatalysts with the larger 2D-2D
coupling interfaces (as shown in Fig. 40a) [151], demonstrating a
more than 3.07-time enhancement of photocatalytic H2 -evolution
activity (using Pt and methanol as cocatalyst and sacricial
agent, respectively). Subsequently, a series of 2D g-C3 N4 -based
layered heterojunctions (e.g. MoS2 [120,290,292,628633], SnS2
[634636], WS2 [637,638], graphene [482,639], SnNb2 O6 [640],
WO3 [287], BiOBr [641], layered double hydroxide [288,642,643],
Bi4 O5 I2 [644] and Bi2 O2 CO3 [645]) have been widely fabricated for
different photocatalytic applications. Among them, g-C3 N4 /MoS2
2D-2D coupling systems have attracted much attention since the
rst report about concept of layered nanojunctions by Hou et al. in
2003 (as shown in Fig. 40b) [120]. It is believed that 2D layered MoS2
can function as co-catalysts [646], stable semiconductor sensitizers
[647] or electron trapper [648,649] in these systems. More inter-

4.7. Co-catalyst loading


The level of the conduction bands of g-C3 N4 is 1.3 V (vs.
NHE), which is more negative than the reduction potentials

of CO2 /CO(0.51 V), H + /H2 (0.41 V), and O2 /O2 (0.33 V),
respectively (As shown in Fig. 41). Thermodynamically, the photogenerated electrons on the CB of g-C3 N4 have much stronger
driving force (or over-potentials) for these three typical kinds of
reduction reactions, as compared to those in TiO2 [28,657,658].
However, the obvious structure defects in bulk g-C3 N4 generally
lead to their fast recombination with the photo-excited holes.
More importantly, the photocatalytic H2 evolution and CO2 reduction are typical up-hill reactions, thus resulting in the sluggish
kinetics on the surface of bulk g-C3 N4 . Fortunately, these disadvantageous factors could be simultaneously overcome by loading
suitable reduction co-catalysts onto the surface of g-C3 N4 , which
could lower the reaction activation energy (or electrochemical
overpotentials), improve the charge separation and transport,
increase stability of photocatalyts, and accelerate the sluggish reaction kinetics of various surface reduction reactions, thus greatly
enhancing the photocatlytic activity [88,124]. Essentially speaking, the single-electron or multi-electron O2 -reduction reactions
(as shown in Table 2) are of signicant importance for photocatalytic degradation [83,410,657], selective organic transformations
[119,244] and disinfection [659,660]. More interestingly, the cocatalysts can also achieve the selective photoreduction products
of CO2 [16,661]. In addition, it is also necessary to deposit suitable hole co-catalysts to accelerate the difcult water oxidation
reactions, due to the lower overpotential of g-C3 N4 for water oxidation (0.59 V), as well as the inherent challenges of four-electron
water oxidation [7,662]. Thus, it is obvious that all these reduction and oxidation co-catalysts play decisive roles in achieving
highly efcient and selective photocatalytic reactions. These four

Fig. 40. Schematic illustration of 2D-2D coupling of g-C3 N4 /graphene (a) and g-C3 N4 /MoS2 (b).

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
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27

Fig. 41. Four kinds of co-catalysts over g-C3 N4 .


Table 6
Summary of various kinds of co-catalysts over g-C3 N4 -based photocatalysts.
Roles/functions of co-catalysts

Noble-metal co-catalysts

Earth-abundant metal co-catalysts

Metal-free and Hybrid co-catalysts


(nano carbons)

H2 evolution

Metal: Pt [663], single-atom Pt


[664]
Suldes: Ag2 S [665]
Plasmonic: Au [666,667], Ag
[479,488]
Bimetallic: PtCo [193], AuPd [194]
Co-loading: Au/Pt [668], Au/PtO
[200]
RuO2 , [44,133]

Ni(OH)2 [126,669], WS2 [637,638],


Cu(OH)2 [521], MoS2
[328,517,628,632], NiSx
[125,197,670673], NiOx , Cu [674],
Ni [675,676], Ni(dmgH) 2 [677],
hollow Zn0.30 Co2.70 S4 [678], [Ni
(TEOA)2 ]Cl2 [679], Co0.04 Mo0.96 S2
[651]
CoOx [285,684], Co(OH)2 [685],
layered double hydroxide (LDH)
[288,686] Co(II) ions [687], Co3 O4
[688,689], Co-Pi [690]
Layered double hydroxide [642]

Graphene [151], carbon black/NiS


[156], carbon QDs [680], CNTs
[681], CNTs/NiS [198], C60, carbon
ber [682], ZIF-8 derived carbon
[683], acetylene black/Ni(OH)2 [155]

Hole co-catalysts

CO2 reduction

Pt [691693], single-atom (Pd/Pt)


[694], ruthenium complex
[695700]

O2 reduction (degradation)

Pt, Au [590], Ag
[433,483,485,488,506,710723],
Ag2 O [724728], Pd [729732],
bimetallic Au/Pt [481], Ag
Quantum Cluster[733]

types of co-catalysts over g-C3 N4 (as shown in Fig. 41), namely,


H2 -evolution, CO2 -reduction, O2 -reduction and H2 O-oxidation cocatalysts, are summarized in Table 6, which will be compared and
discussed in this section in detail.
Similar to those co-catalysts on TiO2 [25], these different cocatalysts over g-C3 N4 -based photocatalysts can be divided into
three categories (as shown in Table 6): noble-metal co-catalysts,
earth-abundant metal co-catalysts, metal-free and hybrid cocatalysts (nano carbons). The nano carbons as co-catalysts will
be highlighted in the next section. Here, we will focus on the
noble-metal and earth-abundant metal co-catalysts, especially for
the latter. As observed from Table 5, it is clear that the more
efforts have been devoted to the developments of H2 -evolution
and O2 -reduction co-catalysts. On the one hand, the noble-metal
co-catalysts (e.g., single-atom [664], bimetallic [193,194,481] and
co-loading [200,668]) seem to be more promising for both photocatalytic H2 -evolution and O2 -reduction reactions, which deserve
more attention in the future studies. On the other hand, for earthabundant metal co-catalysts, the 2D layered co-catalysts, such
as MoS2 [292,328,517,599,628630,632,735], Ni(OH)2 [126,669],
WS2 [637,638], Cu(OH)2 [521], and NiSx [125,197,670673], have

NiO [734], MoS2


[292,599,629,630,735], Fe(III)
[736], H3 BO3 [737], Phosphate
[738,739], Fe (III)/Co(III) [245]

Graphene/LDH [288]

Phosphate [701], graphene


[160,702704], carbon [705], CNTs
[706], S-doped porous carbon
[707], UiO-66 (zirconium-based
MOFs) [708], Co-ZIF-9
(cobalt-based MOFs)[709]
Graphene [220,244,739744],
carbon QDs [745,746], CNTs [747],
biochar [748], PANI [749751], C60
[752,753] graphene/Ag [710,754],
CNTs/Au [755], ordered
mesoporous carbon [756,757]

become the shinning stars in the elds of photocatalytic H2


generation and degradation of pollutants (for O2 reduction),
which will be still the prescriptive research topics in these
elds. In addition, the fabrication of nanostructured hybrid cocatalysts [155,156,198,651,678] and development of molecular
clusters (such as Fe(III)/Co(III) [245,736,758]) and amorphous cocatalysts[759] might become an attractive direction in the near
future.
Relatively speaking, there are only limited reports about
the photocatalytic water oxidation over g-C3 N4 -based photocatalysts modied by Co-based molecules or compounds,
[285,684,685,687689] RuO2 [44,133] or LDH [288,686]. In this
regard, other water-oxidation co-catalysts such as cubic Co complex [760,761], Nocera cobalt phosphate (CoPi) [762,763], IrO2
[764], NiOx [765767], or g-C3 N4 /graphene [262], should be paid
more attention in future studies. Similarly, so far, only few cocatalysts on g-C3 N4 , e.g., Pt-based, [691694] ruthenium complex
[695700], LDH [642], Phosphate [701], MOFs [708,709] and carbon [160,702707], have been available for selective photocatalytic
CO2 reduction. Thus, in future, it is expected that more and more
earth-abundant CO2 -reduction co-catalysts with high activity and

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
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Fig. 42. Roles of carbon materials in enhancing the performance of g-C3 N4 -based
composite photocatalysts [781].

selectivity could be developed and utilized in the production of


solar fuels from the CO2 photoreduction.
4.8. Nanocarbon loading
So
far,
various
kinds
of
carbon
materials,
CNTs
including
[147,198,747,755,768],
graphene
[151,160,288,650,702,703,769773], C60 [752,753], carbon quantum dots [745,774777], carbon bers [682], activated carbon,
carbon black [156,778,779], acetylene black [155], etc. have been
widely coupled with g-C3 N4 to fabricated the g-C3 N4 /carbon
hybrid materials [780]. The essential reasons can be attributed to
the promoted charge separation by the as-formed carbon-based
Schottky-junction between g-C3 N4 and the highly conductive
nano carbon materials and the enhanced adsorption performances
from narrowing band gap due to the carbon doping [25]. More
specically, coupling with various carbon rich materials with
g-C3 N4 not only compensate the disadvantages of individual
semiconductor materials, but also induce the interesting synergetic effects, like supporting material, increasing adsorption and
active sites, electron acceptor and transport channel, cocatalyst,
photosensitization, photocatalyst, and band gap narrowing effect
(as shown in Fig. 42) [781]. Here, we will highlight the hybrids of
g-C3 N4 /graphene, which have been the most widely investigated
g-C3 N4 /carbon composite photocatalysts.
Compared to the 0D and 1D carbon materials, graphene, a
sp2 -hybridized 2D carbon nanosheet, exhibits a much higher
optical transmittance, conductivity (5000 W m1 K1 ), electron
mobility (200,000 cm2 V1 s1 ), theoretical specic surface area
(2600 m2 g1 ) and more suitable work function (4.42 eV) for H2
evolution [17,658,782787]. Thus, the combination of g-C3 N4 and
graphene has been widely shown to be one of promising strategies
to favor the charge transfer and inhibit the charge recombination
process, thereby leading to an enhanced photocatalytic activity for
H2 production. As displayed in Fig. 40a, the 2D-2D coupling interface in the g-C3 N4 /graphene hybrids could achieve much larger
interfacial coupling areas and more efcient charge separation, as
compared to the 0D-2D and 1D-2D hybrids. For example, the doping of g-C3 N4 by graphene could be achieved through formation
of C O C covalent bonding or - stacking interactions, both of
which can effectively narrow the band gap of g-C3 N4 , thus leading
to the enhanced visible-light photocatalytic activity [702,788790].
Recently, based on the state-of-the-art hybrid DFT, Xu et al. systematically investigated the interaction between the g-C3 N4 and RGO
sheets [773]. It was demonstrated that the appropriate O concentration plays a crucial role in altering the direct gap to indirect one.
Most importantly, a higher O concentration could achieve a type-II,
staggered band alignment at the g-C3 N4 -RGO interface, leading to
the high hydrogen-evolution activity over O atoms (as active sites)

Fig. 43. The proposed mechanism for photocatalytic water splitting over the gC3 N4 (electron sink and H2 -evolution site)/RGO-3 composite [773].

in the RGO (Fig. 43) [773]. The ndings pave the way for developing RGO-based composites for photocatalytic applications. At this
point, the semiconductor properties of RGO are more promising
in constructing composite photocatalysts [740], which deserves
more attention in future studies. In addition, doping or co-doping
of RGO materials with heteroatoms has also been demonstrated
to exhibit the signicantly enhanced electrocatalytic performances
[791], which are also highly expected to be utilized in constructing
g-C3 N4 /doped RGO composite photocatalysts.
5. Potential applications of g-C3 N4 -based composite
photocatalysts
5.1. Photocatalytic water splitting
Since the pioneering works by Honda and Fujishima in 1972 [1],
various heterogeneous photocatalysts have been widely applied
in the attracted photocatalytic hydrogen production from water
reduction [7]. Normally, photocatalytic water splitting systems
can be divided into half-reaction water splitting (for H2 and O2 )
and overall water splitting systems [7]. Interestingly, g-C3 N4 has
been extensively applied in these two systems to boost their photocatalytic activity for water splitting. Table 7 summarizes the
photocatalytic activities of g-C3 N4 based photocatalysts for H2
generation on various conditions, including the amount of photocatalysts, the sacricial reagents, H2 generation rate, and the
corresponding quantum efciency in this review. As shown in
Table 7, co-catalysts and sacricial reagents are crucial for achieving the highly efcient photocatalytic H2 evolution, which will be
discussed in detail.
As observed in Table 7, it is clear that the high H2 -evolution
activity over nanostructured g-C3 N4 -based semiconductors is generally obtained via loading the shape-dependent noble-metal Pt
nanoparticles as co-catalysts [315,321,348,445,562,809,819,823].
In the pioneering work, Wang and co-workers found that the
loading 3 wt% Pt as co-catalysts on g-C3 N4 could achieve the H2 evolvtion amount of 770 mol after 72 h in the TEOA aqueous
solution, whereas the bare g-C3 N4 exhibits the negligible H2 production activity. This is due to the rapid recombination of CB
electrons and VB holes, and the large H2 -evolution overpoten-

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
http://dx.doi.org/10.1016/j.apsusc.2016.07.030

structure

synthetic method

co-catal./mass ratio

mass (g)

light source

incident light

aqueous
reaction

cocatal./activity
(mol h1 )

Ni@/g-C3 N4
NiS/g-C3 N4

particles/lamellar
nanoparticles/lamellar

solvothermal method
hydrothermal method

Ni/10 wt.%
NiS/1.25 wt.%

0.05
0.1

quartz reactor
Pyrex reactor

10 vol.% TEOA
15 vol.% TEOA

Ni/8.41
NiS/46

NiS/g-C3 N4

nanoparticles/lamellar

in stiu ion-exchange method

NiS/1.5 mol%

0.1

10 vol.% TEOA

NiS/44.77

[670] (2014)

NiS/e-C3 N4

ultrathin
nanosheets/nanoparticles

NiS/1.0 wt.%

0.05

quartz reactor

10 vol.% TEOA

NiS/4.2

[671] (2015)

Ni(OH)2 /gC3 N4
Ni/NiO/g-C3 N4

nanoparticles/lamellar

liquid
exfoliation-hydrothermal
method
precipitation method

500 W Xe lamp
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
150 W Xe lamp,
> 400 nm

Ni(OH)2 /0.5 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

Ni(OH)2 /7.6

core-shell/lamellar

in situ immersion method

Ni/NiO/2 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

Ni/NiO/10

[792] (2015)

NiS/CNT/mpgC3 N4
NiS/CB/g-C3 N4

nanoparticles/nanotubes/lamellar
sol-gel-precipitation method

NiS/1 wt.%

0.05

quartz reactor

10 vol.% TEOA

NiS/26.05

[198] (2015)

nanoparticles/lamellar

quartz reactor

15 vol.% TEOA

CB, NiS/49.6

[156] (2015)

sub-mircowires/lamellar

CB/0.5 wt.%,
NiS/1.0 wt.%
Ni(dmgH)2 /3.5 wt.%

0.05

Ni(dmgH)2 /gC3 N4
g-C3 N4

physical mixing-chemical
deposition
chemical deposition

0.005

quartz reactor

15 vol.% TEOA

Ni(dmgH)2 /1.18

[677] (2014)

Pt/3 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

Pt/28.55

[793] (2016)

pm-g-C3 N4

porous

co-polymerization-surface
activation-exfoliation
sintering

Pt/3 wt.%

0.1

10 vol.% TEOA

Pt/41.7

[159] (2017)

g-C3 N4

microsphere

solvothermal method

Pt/3 wt.%

15 vol.% TEOA

Pt/1.80

g-C3 N4

lamellar

Pt/1 wt.%

0.1

Pyrex reactor

10 vol.% TEOA

Pt/34

g-C3 N4

ower-like nanorods

heating acetic acid treat


melamine
recrystallization method

Pt/3 wt.%

0.05

quartz reactor

10 vol.% TEOA

Pt/261.8

Pt/0.6 wt.%

0.1

10 vol.% TEOA

Pt/89.28

[794]
(2015)
[795]
(2015)
[428] (2015)

Pt/3 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

Pt/272

[796] (2015)

0.1

350 W Xe arc lamp,


> 400 nm
350 W Xe lamp,
> 420 nm
300 W Xe lamp,
420 nm
300 W Xe lamp,
420 nm
300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W xenon lamp,
> 400 nm
300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 420 nm
300 W Xe arc lamp,
> 400 nm
350 W Xe arc lamp,
> 420 nm
visible light, > 420 nm

Pyrex reactor

10 vol.% TEOA

Pt/502

10 vol.% TEOA

Pt/39.4

quasi-2D-C3 N4 lamellar
mg-C3 N4

mesoporous

melamine-assisted exfoliation
method
calcinating-dissolving method

CNIC

nanotubes

molten salt

Pt/3 wt.%

CNT/g-C3 N4

nanotubes/lamellar

calcinating method

CNT/2 wt.%, Pt/1.2 wt.% 0.1

MVNTs/g-C3 N4 nanotubes/particles

calcinating method

MVNTs/2.0 wt.%

0.1

C/g-C3 N4

ber/lamellar

Pt/1.0 wt.%

0.05

C/g-C3 N4

mixing-calcinating method

carbon black/0.5 wt.%,


Pt/3 wt.%
C-dots/0.25 wt.%

0.1

C-dots/g-C3 N4

nanoparticles/rectangular
nanotube
dots/lamellar

electrospinning and
calcinations method
molten salt method

0.05

CQDs/g-C3 N4

quantum dots/lamellar

hydrothermal method

CQDs, Pt/3 wt.%

0.05

C-dots/g-C3 N4

hydrothermal method
thermal condensation

C-dots/0.2 wt.%,
Pt/0.2 wt.%
C-ZIF/1 wt.%

0.05

C-ZIF/g-C3 N4

nanodots/ultrathin
nanosheets
nanoparticles/lamellar

0.1

N/g-C3 N4

nanosheet

calcinating method

N-doped,Pt/3 wt.%

0.05

C3 N4+x

lamellar

co-thermal condensation

N-doped,Pt/3 wt.%

0.08

1.62 (420 nm)

21.2 (420 nm)

[126] (2013)

[397] (2015)

[106] (2013)
[147] (2014)

quartz reactor

25 vol.% CH3 OH MVNTs/1.15

[681] (2012)

Pyrex reactor

10 vol.% TEOA

[682] (2015)

quartz reactor

25 vol.% CH3 OH C, Pt/69.8

[779] (2014)

Pyrex reactor

25 vol.% CH3 OH 8.6

[797] (2015)

Pyrex reactor

10 vol.% TEOA

Pt/5.805

[680] (2016)

5 vol.% CH3 OH

Pt/88.1

0 vol.% TEOA

C-ZIF/32.58

[777]
(2016)
[683] (2016)

10 vol.% TEOA

Pt/64

[798] (2016)

10 vol.% TEOA

Pt/44.28

[799] (2015)

Pyrex reactor

Pt/54

29

4 UV-LEDs (3 W,
= 420 nm)
400 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 400 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 400 nm

1.1 (420 nm)

[192] (2015)
[125] (2013)

ARTICLE IN PRESS

ultrathin nanosheets

1.9 (440 nm)

reference
(year)

G Model

APSUSC-33598; No. of Pages 52

QY (%)

photocatalyst

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx

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http://dx.doi.org/10.1016/j.apsusc.2016.07.030

Table 7
Summary of the photocatalytic H2 evolution on g-C3 N4 -based photocatalysts.

structure

synthetic method

co-catal./mass ratio

mass (g)

light source

incident light

aqueous
reaction

cocatal./activity
(mol h1 )

P/g-C3 N4

calcinating method

P-doped, Pt/3 wt.%

0.05

10 vol.% TEOA

Pt/104.1

[315] (2015)

copolymerization

P-doped

0.1

Pyrex reactor

10 vol.% TEOA

Pt/50.6

Br/g-C3 N4

lamellar

calcinating method

Br-doped, Pt/3 wt.%

10 vol.% TEOA

Pt/48

[324]
(2015)
[800] (2016)

g-C3 N4

calcinating method

O-doped, Pt/3 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

Pt/60.2

S/g-C3 N4

nanosheets have a porous


network
lamellar

calcinating method

S-doped, Pt/1 wt.%

0.1

quartz reactor

25 vol.% CH3 OH Pt/12.16

[307] (2013)

K-g-C3 N4

lamellar

KCl-template method

K, Pt/0.5 wt.%

0.01

Pyrex reactor

10 vol.% TEOA

[445] (2014)

Zn/g-C3 N4

lamellar

calcinating method

Zn-doped, Pt/0.5 wt.%

0.2

Pyrex reactor

Co-Pi/g-C3 N4

in situ photodepositions

CoPi, Pt/1 wt.%

0.1

Au/g-C3 N4

nanoparticles/aggregated
sheets
nanoparticles/lamellar

Pt/59.5
18.5 vol.%
CH3 OH
25 vol.% CH3 OH Pt/19.48
0.05 M AgNO3
10 vol.% TEOA Au/177.4

AuPd/g-C3 N4

nanoparticles/lamellar

0.05

300 W Xe arc lamp,


> 400 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
420 nm
300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 400 nm
300 W Xe lamp,
> 420 nm
200 W Xe arc lamp,
420 nm
300 W Xe arc lamp,
> 400 nm
125 W Hg lamp,
> 400 nm
300 W Xe arc lamp,
400 nm
300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 400 nm
300 W Xe lamp,

Pyrex reactor

P/g-C3 N4

owers of in-plane
mespores
lamellar

0.1

photodeposition method

0.05

impregnaton method
CsTaWO6 /Au/g- gathered
C3 N4
block/nanoparticles/lamellar
Cd0.5 Zn0.5 S/gnanoparticles/lamellar
hydrothermal method
C3 N4

Au/0.33 wt.%,
Pt/0.40 wt.%
Au/0.5 wt.%

0.08

[194] (2015)

Pyrex reactor

6.2 vol.% TEOA

Pt-Au/17

[350] (2015)

Pyrex reactor

25 vol.% CH3 OH Au/PtO/16.9

[200] (2016)

quartz reactor

20 vol.% CH3 OH Au/0.458

[667] (2015)

Xe lamp, > 420 nm

Pyrex reactor

20.8 mL/h

300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 400 nm
300 W Xe lamp,
> 420 nm
350 W Xe arc lamp,
420 nm

Pyrex reactor

0.35 M Na2 S
and 0.25 M
Na2 SO3
0.1 M Na2 S and
0.1 M Na2 SO3
0.1 M Na2 S and
0.5 M Na2 SO3
0.1 M
L-ascorbic acid
25% vol.%
CH3 OH
10 vol.% TEOA
0.35 M Na2 S
and 0.25 M
Na2 SO3
0.35 M Na2 S
and 0.25 M
Na2 SO3
10 vol.% TEOA

Pt/265.15

3.16 (420 nm)

[348] (2015)

Pt/207.6

4.3 (420 nm)

[562] (2013)

NiS/128.2

[197] (2015)

Ni(OH)2 /115.18 16.7


(450 nm)

[669]
(2016)

MoS2 /2.52

[632] (2015)

37 (425 nm)

[801] (2015)

299.24

7.1 (420 nm)

Pt/22.47

8 (420 nm)

[802]
(2015)
[803]
(2016)
[503] (2013)

0.05

particles/lamellar

hydrothermal method

0.05

QDs/lamellar

in situ hydrothermal method

Pt/0.5 wt.%

0.005

QDs/lamellar

chemical impregnation
method

Pt/1.0 wt.%

0.1

Pt/3 wt.%

0.02

particles/particles

in situ self-transformation
method

Pt/1.0 wt.%

0.05

CdS/g-C3 N4

core/cell nanowires

solvothermal-chemisorption
method

Pt/0.6 wt.%

0.05

350 W Xe arc lamp,


420 nm

Pyrex reactor

nanoparticles/nanorodes/lamellar
in situ hydrothermal method
NiS/CdS/gC3 N4
Ni(OH)2 /CdS/g- core/shell nanorodes
hydrothermal method
C3 N4

NiS/9 wt.%

0.05

quartz reactor

Ni(OH)2 /4.76

0.001

300 W Xe lamp,
420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 400 nm
300 W Xe arc lamp,
> 400 nm

Pyrex reactor

0.25 M Na2 S
and 0.35 M
Na2 SO3
10 vol.% TEOA

quartz reactor

25 vol.% CH3 OH MoS2 , Pt/23.1

in situ light-assisted method

MoS2 /2.89 wt.%

0.01

MoS2 /g-C3 N4

nanoparticles/lamellar

mixing-calcinating method

MoS2 /0.5 wt.%,


Pt/1.0 wt.%

0.1

[666] (2014)

AuPd/16.3

hydrothermal method

ower-like/lamellar

[690] (2013)

10 vol.% TEOA

nanoparticles/lamellar

MoS2 /g-C3 N4

[300] (2011)

quartz reactor

Cd0.2 Zn0.8 S/gC3 N4


CdLa2 S4 /mpgC3 N4
CdS
QDs/g-C3 N4
CdS
QDs/g-C3 N4
CdS
QDs/g-C3 N4
g-C3 N4 /CdS

QDs/hollow

3.2 (420 nm)

quartz reactor
quartz reactor
quartz reactor
Pyrex reactor
Pyrex reactor

quartz reactor

208.8

Pt/17.27

[502] (2012)

Pt/601

[804] (2015)

[628] (2013)

ARTICLE IN PRESS

Au/PtO/g-C3 N4 nanoparticles/lamellar

0.02

Pt/102.8

[321] (2015)

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx

0.05

Pt-Au@ g-C3 N4 lamellar

Au/1 wt.%
deposition-precipitation
method
chemical reduction-calcinating AuPd/0.5 wt.%
method
photodeposition method
Pt, Au

quartz reactor

7.8 (420 nm)

reference
(year)

G Model

QY (%)

photocatalyst

APSUSC-33598; No. of Pages 52

30

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Table 7 (Continued)

synthetic method

MoS2 /CN-Py

ower-like/lamellar

ZnS/g-C3 N4
WS2 /g-C3 N4

QY (%)

mass (g)

light source

incident light

aqueous
reaction

cocatal./activity
(mol h1 )

in suit solvothermal method

0.05

Pyrex reactor

10 vol.% TEOA

25

[805] (2016)

microsphere/lamellar

precipitation method

0.05

Pyrex reactor

25 vol.% CH3 OH 9.7

[806] (2014)

slabs/porous sheet-like

gas-solid reaction

WS2 /0.01 wt.%

0.05

Pyrex reactor

25 vol.% CH3 OH WS2 /5.05

[638] (2015)

WS2 /0.3 wt.%

0.05

Pyrex reactor

10 vol.% TEOA

WS2 /6.12

[637] (2014)

CaIn2 S4 /g-C3 N4 nanoplate-lamellar

impregnation-suldation
method
hydrothermal method

Pt/1.0 wt.%

0.05

Pyrex reactor

nanoparticles/lamellar

H2 reduction

Cu

0.05

0.5 M Na2 S and Pt/5.1


0.5 M Na2 SO3
25 vol.% CH3 OH Cu/1.025

[807] (2015)

Cu/g-C3 N4

300 W Xe lamp,
> 420 nm
4 UV-LEDs (3 W,
= 420 nm)
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
4 UV-LEDs (3 W,
= 420 nm)
Xe lamp, > 400 nm

CuO/g-C3 N4

mono-dispersed
wet impregnation-calcination
sphere/lamellar
method
clusters/spherical particles precipitation method

Pt/1.0 wt.%

0.1

Cu(OH)2 /0.34mol%

0.1

nanoparticles/lamellar

in situ reduction method

Pt/3 wt.%

0.1

CuO2 @g-C3 N4

core@shell octahedra

Pt/3 wt.%

0.3

g-C3 N4 /InVO4

lamellar/nanoparticles

solvothermal and
chemisorption method
hydrothermal method

Pt/0.6 wt.%

0.05

ZnFe2 O4 /gC3 N4
CuFe2 O4 /gC3 N4
FeOX /g-C3 N4

akes/lamellar

calcinating method

Pt/1 wt.%

0.1

nanoparticles/lamellar

calcinating method

Pt/3 wt.%

0.1

granular-like

calcinating method

Pt/3 wt.%, FeOX (20 g


0.1
urea/100 mg ferrocene)
Pt/1 wt.%
0.05

WS2 /mpg-C3 N4 mesoporous nanosheets

N-CeOx /g-C3 N4 nanoparticles/lamellar

one-pot annealing method

Ag2 O/g-C3 N4

nanaosheets

hydrothermal method

0.01

Ag2 S/g-C3 N4

particle/mesopores sheets

precipitation method

0.05

TiO2 /g-C3 N4

yolk-shell spheres/lamellar solvothermal method

0.05

g-C3 N4 /B-TiO2

0.1

CoTiO3 /g-C3 N4

two removed the top of the solvothermal method


pyramids
rods/lamellar
a facial in situ growth method

C,
NTiO2 /g-C3 N4
N,STiO2 /gC3 N4

nanoparticles/ultrathin
nanosheets
semi-spherical
nanoparticles/lamellar

Pt/3 wt.%

0.02

one-pot solvothermal method

0.1

in situ thermal induced


polymerization method

0.05

1% wt.%Pt/TiO2
chemical
g-C3 N4 /PtTiO2 nanoparticles/nanoparticles/lamellar
adsorption-calcinating method
lamellar/nanosheets/nanorodes
hydrothermal method
gC3 N4 /MoS2 /TiO2
hydrothermal method
Pt/1 wt.%
C3 N4 /rGO/WO3 nanosheets/nanosheets/nanoparticles

0.1

W18 O49 /g-C3 N4 nanowires/lamellar

0.005

solvothermal method

Pt/3 wt.%

0.1
0.02

300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 400 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe arc lamp,
> 420 nm
300 W Xe arc lamp,
> 430 nm
300 W Xe lamp,
680 nm > > 420 nm
300 W Xe lamp, 780
nm > > 420 nm
300 W Xe lamp,
> 420 nm
300 W Xe lamp,
> 420 nm
4 UV-LEDs (3 W,
= 420 nm)
4 UV-LEDs (3 W,
= 420 nm)
300 W Xe arc lamp,
> 400 nm
300 W Xe lamp
300 W Xe lamp,
> 400 nm
125 W medium
pressure Hg lamp,
400 nm
300 W Xe lamp,
420 nm
300 W Xe arc lamp,
> 400 nm
250 W iron doped
metal halid UVvis
lamp ( > 420 nm)
300 W Xe arc lamp,
> 420 nm

10 vol.% TEOA

0.35 (420 nm)

Pt/93.7

reference
(year)

[674]
(2016)
[808] (2016)

Pyrex reactor

25 vol.% CH3 OH Cu(OH)2 /4.87

[809] (2014)

Pyrex reactor

10 vol.% TEOA

Pt/24.13

[525] (2014)

Pyrex reactor

10 vol.% TEOA

Pt/79.5

[802] (2015)

20 vol.% CH3 OH Pt/10.6

4.9 (420 nm)

[351] (2015)

Pyrex reactor

10 vol.% TEOA

Pt/20

[439] (2014)

quartz reactor

10 vol.% TEOA

Pt/76

[810] (2016)

quartz reactor

10 vol.% TEOA

FeOX , Pt/108

[811] (2016)

Pyrex reactor

10 vol.% TEOA

Pt/14.62

[812] (2015)

Pyrex reactor

10 vol.% TEOA

33.04

[813] (2015)

Pyrex reactor

20 vol.% CH3 OH 10

[665] (2014)

Pyrex reactor

25 vol.% CH3 OH 5.6

[814] (2016)

Pyrex reactor

25 vol.% CH3 OH 47.3

[815] (2016)

quartz reactor

10 vol.%
C2 H5 OH
10 vol.% TEOA

3.92

[817] (2015)

10 vol.% TEOA

317

[818]
(2015)

Pyrex reactor

10 vol.% TEOA

Pt/178

[819] (2012)

Pyrex reactor

25 vol.% CH3 OH 125

Pyrex reactor

deionized
water

Pt/2.84

0.9 (420 nm)

[820]
(2016)
[821] (2015)

quartz reactor

10 vol.% TEOA

Pt/3.69

1.79 (400 nm)

[822] (2016)

38.4 (365 nm)

[816] (2016)

31

Co-Pi: cobalt-phosphate; MVNTS: multi-walled carbon nanotubes; py:pyridine; CNIC: carbon nitride intercalation compound; C-ZIF: ZIF-8 derived.

Pt/11.7

ARTICLE IN PRESS

Cu(OH)2 /gC3 N4
CuO2 /g-C3 N4

co-catal./mass ratio

G Model

structure

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photocatalyst

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Table 7 (Continued)

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Fig. 44. The photocatalytic H2 -evolution rate over g-C3 N4 modied by Pt cocatalysts with different shapes [823].

tial over pure g-C3 N4 . Subsquently, various engineering strategies,


highlighted in the section 4, have been employed to enhance the
H2 evolution activity over the g-C3 N4 /Pt systems [369,395,396]. For
example, Wang and coworkers demonstrated that nanospherical
g-C3 N4 frameworks, with interconnecting nanosheets and highly
open-up spherical surfaces with sharp edges, achieved an AQY of
9.6% at 420 nm for H2 evolution [369]. More recently, Cao et al. also
demonstrated that the spherical Pt nanoparticles on g-C3 N4 exhibiter much better H2 -evolution activity than those of octahedral
and cubic Pt nanoparticles on g-C3 N4 , due to its favorable exposed
facets, disparity and adsorption energies induced by the spherical shape (as shown in Fig. 44) [823]. More interestingly, it was
also demonstrated that the single-atom Pt co-catalyst on g-C3 N4
exhibited a 8.6-fold enhancement in photocatalytic H2 -evolution
activity, as compared to that of Pt nanoparticles-loaded g-C3 N4 ,
due to the maximized atom efciency and improved surface trap
states [664]. Unfortunately, their high cost and low stability significantly limit their practical application in a large scale. Therefore,
design and preparation of advanced alternative co-catalysts with
excellent performance and low cost are of great importance for
the development of these photocatalytic systems. Accordingly,
the earth-abundant rst-row transition metal electrocatalysts,
including Fe-, Co-, Ni- and Cu-based co-catalysts have been of
increasing interest in both electrocatalysis and photocatalysis in
the recent years [124,272274,824]. Importantly, loading suitable
earth-abundant co-catalysts onto the g-C3 N4 provides a facile and
strategy to construct real robust g-C3 N4 -based H2 -evolution photocatalytic systems. Here, we will highlight the unique Ni-based
co-catalysts for enhancing the activity of the g-C3 N4 semiconductor.
To date, various kinds of Ni-based co-catalysts, including Ni [192,675,676,825], Ni(OH)x [126,155,669], NiSx
[125,156,197,198,670,672,673], [Ni(TEOA)2 ] Cl2 [679], NiOx
[734,792], and Ni(dmgH)2 [677,826] have been widely employed
as co-catalysts to accelerated the photocatalytic activity of the
g-C3 N4 for different applications [272]. For example, Yu et al.
demonstrated that the as-fabricated 0.5 mol% Ni(OH)2 -modied
g-C3 N4 composite photocatalysts exhibited the highest H2 production rate of 7.6 mol h1 (with an AQE of 1.1% at 420 nm, as
shown in Fig. 45a), approaching that of optimal 1.0 wt% Pt/g-C3 N4
(8.2 mol h1 ), due to the promoted charge separation and surface
reaction rate induced by the loading of Ni(OH)2 (as shown in
Fig. 45b) [126]. This work perfectly highlighted the promising utilization of low cost Ni(OH)2 as a substitute for noble metals (such
as Pt) in the photocatalytic H2 production for g-C3 N4 . Following
this work, Li and co-workers recently demonstrated that the dual

electron co-catalysts of robust acetylene black and Ni(OH)2 could


signicantly enhance the photocatalytic H2 -evolution activity over
g-C3 N4 /Ni (OH)2 hybrid systems. When inserting 0.5% acetylene
black into the interface regions between Ni(OH)2 and g-C3 N4 , a 3.31
time enhancement in H2 -evolution activity can be thus achieved.
It is suggested that the enhanced activity can be attributed to the
effectively promoted separation of photo-generated electron-hole
pairs and enhanced the following H2 -evolution kinetics [155].
Especially, various cheap nanoconbons should be fully integrated
with robust co-catalysts and g-C3 N4 to maximize the functions of
co-catalyst and g-C3 N4 semiconductor.
In addition, several other highly efcient ternary g-C3 N4 -based
photocatalysts have also been developed recently, For instance, Li
and co-workers conrmed that the CdS photosensitizer and NiS
co-catalysts in ternary g-C3 N4 -CdS-NiS composites play key roles
in boosting the H2 -generation acticity of g-C3 N4 under visiblelight illumination [197]. The highest H2 -production activity of
2563 molg1 h1 is about 1528 times as high as that of the pure
g-C3 N4 (Fig. 46). In another work, when inserting carbon black into
the interfaces between g-C3 N4 and NiS, the average H2 -evolution
rate of g-C3 N4 /0.5%CB/1.5%NiS can reach 992 mol g1 h1 , which
is about 2.51-fold higher than that of g-C3 N4 /1.5%NiS with a photocatalytic H2 production rate of 395 mol g1 h1 (Fig. 47) [156].
In another paper by Li and co-workers, mpg-C3 N4 /CNT/NiS was
synthesized via the sol-gel method and the direct precipitation process [198]. The results show that the mpg-C3 N4 /CNT/NiS composite
exhibits the highest H2 -evolution rate of 521 mol g1 h1 , which
is about 148 times as high as that of mpg-C3 N4 /CNT. These results
highlighted that the ternary hybrid should be a promising direction for constructing highly efcient earth-abundant g-C3 N4 -based
composite H2 -evolution photocatalysts.
However, there are few attempt reported to reveal the nature
and structural features of the Ni co-catalyst as well as the possible structural and bonding situation occurring at the co-catalyst
active sites under light irradiation [676]. To achieve this aim, in situ
EPR measurements (Fig. 48a) conrmed that a continuous increase
of the Ni0 signal was detected (though, not all Ni2+ species were
reduced to Ni0 at the same time), indicating the Ni0 acts as the HER
active sites during the photocatalysis (Fig. 48b) [676]. For other
Ni species, although the electrochemical performances, including polarization curves, time dependence of the current density,
and electrochemical impedance spectroscopy of g-C3 N4 have been
widely determined [197], the accurate catalytic mechanism still
needs to be uncovered in future. Therefore, both the deep mechanism studies and continuous efforts in developing new co-catalysts
are highly expected, to achieve the rational design of highly efcient
Ni-based co-catalysts modied g-C3 N4 photocatalysts for practical
applications.
Finally, it should be pointed out that the oxidation half
reaction of g-C3 N4 should be paid more attention, which is crucial for improving the photocatalytic H2 -evolution activity and
deeply understand the underlying mechanism for water splitting
[444,685687]. Clearly, constructing the practical g-C3 N4 -based
overall water splitting systems is still very challenging. Recently,
Kang and coworkers demonstrated that the metal-free carbon
nanodotscarbon nitride nanocomposite exhibited the impressive performance for photocatalytic solar water splitting [774].
The measured quantum efciencies of 16% (420), 6.29% (580 nm),
and 4.42% (600 nm), correspond to an overall solar energy conversion efciency of 2.0%. It was veried that carbon dots-C3 N4
catalyzes water splitting to hydrogen and oxygen via the stepwise
two-electron/two-electron two-step pathway under visible light
irradiation. The composite nature of the catalyst provides sufcient proximity between the H2 O2 generation sites on the C3 N4
surface and the carbon dots so that H2 O2 decomposition and O2
generation in the second stage become efcient [774]. This work

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Fig. 45. (a) Comparison of the photocatalytic H2 -production activity of the Nix (x, Ni(OH)2 to (g-C3 N4 + Ni(OH)2 ) was 0, 0.1, 0.5, 1.0, 1.6, and 10 (mol%))and Pt-deposited
g-C3 N4 samples in triethanolamine aqueous solution. (b) Charge separation mechanisms in the Ni(OH)2 /g-C3 N4 system under visible light [126].

Fig. 46. (A) Time courses and (B) the average rate of photocatalytic H2 evolution over the photocatalysts: (a) g-C3 N4 ; (b) g-C3 N4 -CdS; (c) g-C3 N4 -9%NiS; (d) CdS-9%NiS; (e)
g-C3 N4 -CdS-3%NiS; (f) g-C3 N4 -CdS-6%NiS; (g) g-C3 N4 -CdS-9%NiS; (h) g-C3 N4 -CdS-12%NiS; (i) g-C3 N4 -CdS-15%NiS [197].

Fig. 47. (A) The average rate of H2 evolution and (B) proposed charge transfer mechanisms in the g-C3 N4 /CB/NiS composite under visible light irradiation: A g-C3 N4 , B
g-C3 N4 -0.5% CB, C g-C3 N4 -1.5% NiS, D g-C3 N4 -0.5%CB-1.5%NiS, E g-C3 N4 -1.0% CB-1.5% NiS, F g-C3 N4 -1.5% CB-1.5% NiS, G g-C3 N4 -1.5% NiS-0.5% CB [156].

Fig. 48. (a) In situ EPR studies of a suspension of Cat-1 in TEOA solution under continuous visible-light irradiation with increasing the time. (b) Charge separation in sg-CN
and the formation of Ni0 nanoparticles during photocatalysis [676].

demonstrated that the control of oxidation half reaction played key


roles in achieving the overall water splitting. More recently, Wang
and coworkers discovered the irradiated g-C3 N4 loaded by Pt, PtOx ,
and CoOx as redox cocatalysts, can split pure water without the use
of sacricial reagents, while pure g-C3 N4 is virtually inactive for
overall water splitting by photocatalysis [827]. In addition, the liq-

uid state Z-scheme systems, including the g-C3 N4 (3 wt% Pt)/WO3


(0.5 wt% Pt)/NaI (5 mM) and g-C3 N4 (3 wt% Pt)/BiVO4 /FeCl2 (2 mM),
have proven to achieve the overall water splitting [828]. However,
in these systems, the Pt and PtOx are still the noble metal. Thus, it
is clear that developments of low-cost kinetic promoters for both

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H2 and O2 evolution are still the major bottleneck for achieving the
practical H2 evolution or overall water splitting on g-C3 N4 .
5.2. Photocatalytic degradation of pollutants
With rapid growth of population and accelerating industrialization, the environmental contamination has become a major
threat to public health all over the world. Since the rst report
on heterogeneous photocatalytic remediation of environmental
pollutants (CN in water) on titania by Frank and Bard in 1977
[829], the heterogeneous photocatalysis has been widely used
in widespread environmental purication such as air and water
purication [309,830839]. Furthermore, a variety of ways for
increasing the photodecomposition efciency of pollutants over
g-C3 N4 -based semiconductors have been exploited [9,11,20,840],
which have been summarized in Table 8.
As observed in Table 8, constructing the g-C3 N4 -based semiconductor heterojunction and loading suitable O2 -reduction
co-catalysts are the general two strategies to achieve the improved
photocatalytic degradation activity, which will be discussed in this
section. It is clear that the OH radicals in g-C3 N4 -based photocatalysts mainly originated from multi-electron O2 reduction reactions
driven by photo-generated electrons on the CB of g-C3 N4 , because
the photo-generated holes exhibited much negative potentials
(1.4 V) than that of OH/OH (+2.29 V, vs NHE, pH = 7), leading to the
failure in driving the oxidation reaction of adsorbed OH groups to
OH radicals [83,410]. Thus, for improving the photocatalytic activity of g-C3 N4 , more efforts have been devoted to strengthening the
decisive O2 -reduction reactions.
On the one hand, the photocatalytic degradation of gas-phase
pollutants over g-C3 N4 -based photocatalysts has been extensively
investigated, such as NOx [144,883,884], formaldehyde [523],
acetaldehyde [539,885] and so forth. For example, Dong and
coworkers deposited the monodispersed plasmonic Ag nanoparticles onto g-C3 N4 nanosheets to extend visible-light absorption,
increase the generation of O2 and enhance the charge separation, thus achieving the enhanced the photocatalytic activity of
g-C3 N4 nanosheets towards oxidation of NO to nal products [884].
Katsumata et al. demonstrated that WO3 /g-C3 N4 heterojunction
photocatalysts showed a 1.4 times enhancement in photodegradation of acetaldehyde gas, as compared to pristine g-C3 N4 [539]. In
another paper by Yu et al., a direct TiO2 /g-C3 N4 Z-scheme photocatalyst without an electron mediator (as shown in Fig. 38) exhibited
a high photocatalytic performance in the oxidation decomposition
of formaldehyde in air [523]. In these studies, the enhancement
in photoactivity was primarily accredited to the improved transfer
and separation of photogenerated charge carriers and promoted O2
reduction. A mechanically mixed g-C3 N4 and TiO2 sample with similar content did not remarkably improve the conversion of NOx , thus
conrming that the interaction between g-C3 N4 and P25 is vital
for the enhanced activity. EPR measurements once again indicated
that O2 was the main active species involved in the oxidation
of NO under both visible and UV light irradiation [886]. In addition, it should be noted that the adsorption of gas-phase pollutants
on the g-C3 N4 should be carefully optimized to achieve the ideal
photocatalytic degradation efciency.
On the other hand, the g-C3 N4 -based photocatalysts have
been widely used in the photocatalytic degradation of liquidphase pollutants, such as MB [319,506,734,843,887893],
MO
[314,330,576,580,617,688,894898],
RhB
[324,330,742,857,858,872,899906] and so forth. As observed
in Table 8, in pure g-C3 N4 -based visible-light systems, the two
main reactive species, O2 and h+ species, are generally involved
in the degradation of pollutants. Interestingly, besides the aforementioned two species, the presence of OH radicals in Ag/g-C3 N4
systems further provides the direct evidence for its increased

catalytic performance [489]. The further enhanced photocatalytic


activity was observed over the Z-scheme Ag@AgBr/g-C3 N4 plasmonic photocatalyst. It is believed that the Z-scheme system
retained the photoinduced electrons and hole with strong reduction and oxidation power in the CB of g-C3 N4 and VB of AgBr,
respectively, thus achieving the high efcient photodegradation
of MB. During the photocatalysis, the generated Br0 atoms and
superoxide radicals with high oxidizing capabilities are favorable
for the further enhancement in the degradation reaction [486].
Furthermore, it is also noted that the g-C3 N4 -based heterojunctions are widely used in the photocatalytic degradation, whereas,
few systems were further loaded by co-catalysts. For those systems
loaded by co-catalysts, the expensive Ag- and Pt-based co-catalysts
are widely chosen. At this point, the atomically dispersed noblemetal co-catalysts with much stronger metal-g-C3 N4 interactions
are considerably promising for the applications of photodegradation [664,694,907]. Therefore, it is expected that more and more
earth-abundant co-catalysts and other modication strategies can
be applied in the photocatalyctic degradation of liquid-phase pollutants. The homogeneous molecular systems [908] and metal-ion
clusters (such as Fe(III) and Cu (II)) [909916] with the maximum
atom utilization efciency are highly appealing as co-catalysts for
applications in the photodegradation of pollutants over g-C3 N4 based photocatalysts. Whats more, the deep investigation on the
degradation mechanism is also extremely expected. Similar to
TiO2 -based semiconductors, particular attention should be focused
on the investigations on the tunable photocatalytic selectivity of
g-C3 N4 -based photocatalysts towards decomposition of pollutants
with positive/negative charge carriers through precisely controlling the surface charge properties of g-C3 N4 [217219]. In addition,
the interesting photocatalytic degradation of antibiotics over gC3 N4 -based multi-junctions and deep mechanisms also deserve
more attention in the near future [481,744,917919].
5.3. Photocatalytic carbon dioxide reduction
From the viewpoint of development of sustainable energy, conversion of the rapidly increasing greenhouse gases to valuable
energy-bearing compounds (such as CO, methane, and methanol)
using solar energy would be one of the best solutions to overcome
both serious problems of the global warming and shortages of fossil fuels. Therefore, since the rst demonstration of photocatalytic
CO2 reduction by Inoue and co-workers in 1979 [920], signicant
advancements have been made in exploiting efcient and feasible semiconductors for reduction of carbon dioxide with water
during last two decades [16,18,921925]. Among these semiconductor materials, the g-C3 N4 -based photocatalysts have attracted
an increasing interesting in selective photocatalytic conversion of
CO2 to hydrocarbons or chemicls, due to its excellent stability, sufciently negative CB levels, innocuity and low price [17,19,658].
Signicant progresses were summarized in Table 9, which will thoroughly discussed in this section.
On the one hand, various strategies such as loading co-catalysts
and nanocarbons, doping, constructing Z-scheme and heterojunction, have been widely used to enhance the photocatalytic activity
for CO2 reduction [704,940,941]. For example, Yu et al. demonstrated that the Pt content showed a signicant inuence on both
the activity and selectivity of g-C3 N4 for photocatalytic reduction of
CO2 into CH4 , CH3 OH and HCHO (Fig. 49a) [691]. It is believed that
the Pt cocatalyst not only facilitates the interfacial electron transfer from g-C3 N4 to Pt NPs (as shown in Fig. 49b), but also lower
the overpotential for the CO2 reduction. More recently, Maeda and
his coworkers fabricated the Ru complex decorated g-C3 N4 photocatalysts through the continuous stirring of a methanol solution
containing two materials at room temperature overnight [695]. The
resulting heterogeneous photocatalyst systems could achieve the

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Degradation
time/
efciency

calcinating method

0.1

RhB/1 105 M/100 mL

40 min/99%

TiO2 In2 O3 @g- nanoparticles/


C3 N4
nanoparticles- lamellar
CaIn2 S4 /g-C3 N4 nanoplate/lamellar

solvothermal method

0.08

RhB/0.01 g L1 /80 mL

60 min/100%

hydrothermal method

0.05

MO/0.01 g L1 /100 mL

SiO2 /g-C3 N4

core-shell nanosphere

calcinating method

0.07

g-C3 N4 /TiO2

lamellar/particles

sol-gel method

0.1

TiO2 /g-C3 N4

core-cell

self-assembly method

0.05

TiO2 /g-C3 N4

mesoporous
melt-inltrating-calcinating
spheres/lamellar
method
yolk-shell spheres/lamellar solvothermal method

Synthetic method

In2 O3 /g-C3 N4

particles/lamellar

TiO2 /g-C3 N4
g-C3 N4 /TiO2

lamellar/nanoparticles

g-C3 N4 /TiO2

lamellar/roundish particles sol-gel method

g-C3 N4 /TiO2
g-C3 N4 /F-TiO2 lamellar

Co-catal./optimized
mass ratio

0.05
0.01

calcinating method

0.1
0.04

hydrothermal-calcination
method
hydrothermal method

gC3 N4 /Ag/TiO2
K-Na/g-C3 N4

lamellarparticles/microspheres
lamellar

photodeposition-Physical
mixing method
calcinating method

mg-C3 N4

mesopores

calcinating-dissolving method

0.03
0.1
Ag/2 wt.%

0.03

K-Na co-doped

0.05

0.05

g-C3 N4

lamellar

thermal condensation

0.02

mg-C3 N4

mesoporous

calcinating dissolving method

0.05

C60 /mg-C3 N4

particles/lamellar

calcinating method

C60 /0.03 wt.%

0.025

CDs/g-C3 N4

dots/lamellar

mixing-calcinating method

carbon dots/0.5 wt.%

0.05

C-dots/g-C3 N4 dots/lamellar

mixing-calcinating method

C-dots/0.25 wt.%

0.1

Pd/mpg-C3 N4

particles/mesoporous

chemical reduction

Pd-doped/1.5 wt.%

Pt/C3 N4

nanoparticles/nanotubes

hydrothermal method

Pt/2 wt.%

0.1

Au/Pt/g-C3 N4

particles/lamellar

photodeposition method

Au/2 wt.%, Pt/0.5 wt.%

0.1

Au/g-C3 N4 /Fe2 O3

particles/lamellar/
rhombohedral-like

hydrothermal and
ultrasonication method

Au

0.05

300 W halogen
tungsten lamp,
> 400 nm
350 W xenon arc lamp,
> 420 nm
500 W tungsten lamp,
> 400 nm
300 W xenon lamp,
400 nm
500 W xenon lamp,
> 420 nm
500 W xenon lamp,
UVvis light
500 W xenon lamp,
> 400 nm
350 W xenon arc lamp,
> 420 nm
2 150 W tungsten
lamp, > 420 nm
400 W halide lamp,
> 400 nm
300 W xenon lamp,
> 420 nm
50 W LED light,
= 410 nm
300 W xenon lamp,
> 420 nm
250 W high-pressure
sodium lamp,
420 < < 800 nm
300 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 400 nm
500 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
3 W LED lamp,
= 365 5 nm
350 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
500 W xenon lamp,
> 400 nm
halogen lamp

Kapp
[102 min1 ]

Main active
species

Ref. (year)

O2 , OH

[841] (2014)

OH

[797] (2015)

120 min/90%

O2 , h+

[807] (2015)

RhB/0.01 g L1 /70 mL

150 min/94.3%

OH, h+

[842] (2015)

MB/0.01 g L1 /100 mL

360 min/92%

h+

RhB/10 ppm/200 mL

80 min/82%

RhB/0.01 g L1 /50 mL

140 min/100%

RhB/0.01 g L1 /80 mL

150 min/99.3% 33.5

60 min/95%

150 min/100%

h+

[436] (2014)

h+

[847]
(2016)
[655] (2014)

ciprooxacin//0.01 g L
100 mL
RhB/0.01 g L1 /40 mL

4.6

[843] (2016)

4.4

[844] (2015)
[845] (2016)

acyclovir/10 ppm/100 mL

90 min/100%

1.57

MB/0.01 g L1 /100 mL

60 min/89%

3.74

O2 , h+
+

[814] (2016)

OH, h , e

MO/0.0135 g L /30 mL
240 min/94%
phenol/0.0166 g L1 /30 mL 240 min/96%
RhB/1 105 M/200 mL
120 min/90%

RhB/0.005 g L1 /100 mL
4

2,4,6-TCP/10

M/20 mL

[846] (2015)

[848] (2014)
0.86

O2 , OH

180 min/100% 1.17

20 min/95%

[336] (2015)

[849] (2015)
O2 , OOH

[850] (2013)

MO/0.01 g L1 /100 mL

120 min/90%

MB/1 105 M/50 mL


phenol/5 106 M/50 mL
phenol/0.01 g L1 /50 mL

300 min/100% 1.73


0.15
300 min/46%
200 min/100%

RhB/1 105 M/100 mL

60 min/84%

O2

[745] (2016)

BPA/0.02 g L1 /50 mL

360 min/100% 1

O2

[729] (2013)

PCP/0.02 g L1 /100 mL

420 min/98%

TC-HCl/0.02 g L

/100 mL

RhB/0.004 g L1 /250 mL

180 min/93%

15.13

1.3

[796] (2015)
OH, h+

[753] (2014)
[851] (2016)

[852] (2015)
42.86

[481] (2015)

3.16

[853] (2015)

ARTICLE IN PRESS

Targe pollutant/
concentration/volume

Structure

G Model

APSUSC-33598; No. of Pages 52

Mass (g) Light source

Photocatalyst

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx


35

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
http://dx.doi.org/10.1016/j.apsusc.2016.07.030

Table 8
Summary of the photocatalytic degradation of pollutants over g-C3 N4 -based photocatalysts.

physically mixing method

0.025
0.05

MB/1 105 M/50 mL


MB/1 105 M/100 mL

150 min/100% 2.05

13.5

0.02
0.1

MB/1 106 M/30 mL


RhB/2.5 105 M/250 mL

90 min/98.3%
270 min/99%

1.54

OH

particles/lamellar

hydrothermal method
precipitation and reuxing
method
mixing-calcinating method

500 W xenon lamp,


> 420 nm
500 W xenon lamp,
= 254 nm
mild UV light
50 W LED lamp

RhB/0.01 g L1 /100 mL

120 min/97%

3.8

O2 , h+

particles/lamellar

mixing-calcinating method

0.05

300 W xenon lamp,


420 < < 800 nm
250 W xenon lamp,
> 420 nm
200 W xenon lamp

[854] (2015)
[535]
(2015)
[855] (2015)

RhB/0.01 g L1 /100 mL

60 min/95.5%

4.91

O2 , h+

[616] (2016)

350 W xenon lamp,


> 420 nm
350 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
500 W tungsten light
lamp, > 420 nm
300 W xenon lamp,
400 < < 680 nm
250 W halide lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
400 W metal halide
lamp, > 420 nm
300 W xenon lamp,
400 nm
300 W xenon lamp,
400 nm
500 W xenon arc lamp,
> 420 nm
300 W xenon lamp,
400 < < 700 nm
500 W xenon lamp,
> 420 nm
500 W xenon lamp,
> 400 nm
300 W xenon lamp,
> 420 nm
500 W xenon lamp,
> 420 nm
500 W tungsten light
lamp, > 400 nm
500 W xenon lamp,
400 nm
500 W xenon lamp,
> 420 nm
300 W xenon arc lamp,
> 420 nm

RhB/0.01 g L1 /300 mL

120 min/96.7% 4.34

O2 , h+

[856]
(2015)
[857] (2013)

RhB/0.01 g L1 /300 mL

120 min/100% 3.45

[858] (2013)

MO/10 ppm/100 mL

180 min/73%

0.78

[859] (2014)

MB/0.01 g L1 /80 mL

240 min/99%

1.73

MO/0.01 g L1 /100 mL
PNP/0.01 g L1 /100 mL
RhB/0.01 g L1 /100 mL

120 min/100%
120 min/100%
120 min/96%
2.52

atrazine/100 ppm/500 mL

60 min/99%

RhB/0.005 g L1 /100 mL

100 min/99.5% 5.56

MO/0.02 g L1 /50 mL
phenol/0.02 g L1 /50 mL
RhB/0.005 g L1 /100 mL

30 min/90%
180 min/82%
40 min/100%

10.53

1.4

h+

19.54

BF/0.02 g L1 /50 mL
90 min/100%
Bisphenol/0.02 g L1 /50 mL 90 min/85%
1
MO/0.02 g L /40 mL
60 min/100%

5.52
2.08
4

90 min/88%
tetracycline/0.02 g L1 /100 mL

2.18

O2 , h+

[865] (2016)

180 min/90.45%

OH, h+

[506] (2014)

/100 mL

90 min/88.2%

O2 , h

[866] (2016)

RhB/1 105 M/50 mL

240 min/46%

OH, h+

[867] (2015)

RhB/0.01 g L1 /50 mL
phenol/0.01 g L1 /50 mL
MO/0.02 g L1 /100 mL

80 min/95.8%
180 min/76.1%
120 min/100% 0.77

ZnO@mpgC3 N4

core-shell

ZnO/g-C3 N4
gC3 N4 /ZnO/AgCl
Zn2 SnO4 /gC3 N4
V2 O5 /g-C3 N4

owerlike/lamellar
lamellar/particles

g-C3 N4 /V2 O5

lamellar/nanoparticles

Co-catal./optimized
mass ratio

0.2

one-pot method

0.05

GdVO4 /g-C3 N4 small particles/big particles mixing-calcinating method

0.3

g-C3 N4 /SmVO4 lamellar/aggregated


particles
lamellar/nanoparticles
g-C3 N4 /SnO2

mixing-calcinating method

0.3

mixing-calcinating method

0.1

SnNb2 O6 /gC3 N4
Ag/g-C3 N4

nanosheets/lamellar

mixing-calcinating method

0.02

particles/lamellar

photodeposition method

AgI@ g-C3 N4

0.1

precipitation method

0.1

AgCl@pg-C3 N4 nanoparticles/lamellar

modied precipitation method

0.2

Ag3 VO4 /g-C3 N4 particles/lamellar

deposition-precipitation
method
precipitation method

0.05

g-C3 N4 /Ag2 O

core-shell

Ag/2 wt.%

particles/lamellar

Ag2 O/g-C3 N4

nanoparticles/lamellar

coprecipitation method

Ag@g-C3 N4

core-shell

reuxing method

in situ ion exchange method


nanoparticles/lamellar
Ag@AgCl/gC3 N4
AgVO3 /g-C3 N4 nanoribbons/ultrathin
in situ hydrothermal method
nanosheets
Ag3 PO4 /g-C3 N4 spherical particles/lamellar chemisorptions method
Ag/Fe3 O4 /gC3 N4
g-C3 N4 /CdS

0.02
0.1
Ag/0.5 wt.%

0.025
0.025
0.05
0.02

particles/nanoclusters/lamellar
hydrothermal-photodeposition Ag/3 wt.%, Fe3 O4 /9 wt.% 0.05
method
lamellar/nanotube
precipitation method
0.08

QDs/lamellar
CdS
QDs/npg-C3 N4
CdWO4 /g-C3 N4 nanorods/lamellar

mixing-calcinating method

0.1

mixing-calcinating method

0.05

Cd0.2 Zn0.8 S/g- nanoparticles/lamellar


C3 N4
BiPO4 /mg-C3 N4 nanorods/mesoporous

hydrothermal method

0.05

in situ method

0.1

RhB/0.01 g L

/50 mL

MB/0.025 g L1 /200 mL
1

RhB/0.01 g L

Main active
species

Ref. (year)

[533] (2014)

80 min/100%

MB/1 105 M/50 mL


RhB/0.01 g L1 /100 mL

Kapp
[102 min1 ]

30 min/100%

O2 , h+

[640] (2016)

[489] (2013)

O2 , h+

O2 , h+ , OH [860] (2015)
[861] (2015)
O2 , h+ , OH [862] (2015)
[728] (2013)

0.27

O2 , h

[726] (2014)
[488] (2014)

O2 , h+

OH, h+
OH, h+
h+

[433] (2014)
[863] (2015)

[864] (2014)

[802] (2015)
[868] (2014)

ARTICLE IN PRESS

Degradation
time/
efciency

Synthetic method

G Model

Targe pollutant/
concentration/volume

Structure

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx

Mass (g) Light source

Photocatalyst

APSUSC-33598; No. of Pages 52

36

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
http://dx.doi.org/10.1016/j.apsusc.2016.07.030

Table 8 (Continued)

Structure

Synthetic method

BiOCl/C3 N4

owerlike/amorphous

solvothermal method

g-C3 N4 /BiOBr

lamellar/nanosheets

BiOx Iy /g-C3 N4

Mass (g) Light source

Targe pollutant/
concentration/volume

Degradation
time/
efciency

0.2

MO/0.01 g L1 /500 mL

80 min/95%

RhB/0.06 g L1 /40 mL
2,4-DCP/0.01 g L1 /40 mL
CV/10 ppm/100 mL

100 min/98%
180 min/80%
36 h/99%

4.01
3.91
0.283

RhB/1 105 M/50 mL

240 min/56%

17

O2 , h+

MO/0.01 g L1 /200 mL

180 min/94.82%1.66

deposition-precipitation
method
square thin-plates/lamellar controlled hydrothermal

0.02
0.04
0.01

lamellar/plates

mixing-calcinating method

0.05

lamellar/nanosheets

hydrothermal method

0.4

QDS-lamellar

in situ method

0.05

agglomeration

mixing-calcinating method

0.15

lamellar-hollow sphere

hydrothermal method

0.02

lamellar-akelike

hydrothermal method

0.1

lamellar/particles

ball milling

2gL

small particles/big particles mixing-calcinating method

CuTCPP/g-C3 N4 rodlike/lamellar

0.3

ethanol dispersion method

g-C3 N4 /CuOx lamellar/nanoparticles


nanoparticles
-Fe2 O3 /gC3 N4
[WO4 ]2 /glamellar
C3 N4
nanorods/lamellar
WO3 /g-C3 N4
H3 PW12 O40 /C3 Nparticles/tubular
4
NTs
g-C3 N4 /MoO3 lamellar/broader particles

mixed solvent-thermal method


in situ growth strategy method

lamellar/nanoparticles
gC3 N4 /Bi2 MoO6
MoS2 /g-C3 N4 nanosheets/lamellar

calcinating method

0.025
0.01
0.2
[WO4 ]2 doped

0.1

mixing-calcinating method
hydrothermal method

0.05
0.2

mixing-calcinating method

0.1

solvothermal method

0.03
0.04
Ce-doped

0.05

CoO4 -doped/0.2 wt.%

0.1

Ce/g-C3 N4

lamellar

impregnation and calcinating


method
calcinating method

CoO4 /g-C3 N4

lamellar

mixing and heating method

NiO/g-C3 N4

nanoparticles/lamellar

calcinating method

0.05

300 W xenon arc lamp,


> 400 nm
400 W halogen lamp,
> 400 nm
100 W xenon arc lamp
1000 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 400 nm
300 W xenon lamp,
400 nm
500 W xenon lamp,
> 420 nm
400 W metal halide
lamp, 420 nm
400 W xenon lamp,
> 400 nm
500 W xenon lamp,
> 420 nm
400 W
halogen-tungsten
lamp, > 420 nm
500 W xenon lamp,
> 420 nm
350 W xenon lamp
300 W xenon arc lamp,
> 420 nm
300 W xenon lamp,
> 420 nm
500 W tungsten lamp
300 W xenon lamp,
> 420 nm
300 W xenon lamp,
> 400 nm
50 W LED light,
= 410 nm
300 W xenon lamp,
> 400 nm
250 W high-pressure
sodium lamp,
400 < < 800 nm
250 W xenon lamp,
> 420 nm
500 W xenon lamp,
> 420 nm

RhB/0.01 g L

/50 mL

30 min/100%

Kapp
[102 min1 ]

16.8

MO/0.01 g L1 /50 mL

180 min/99.9% 3.66

RhB/0.01 g L1 /50 mL

70 min/98%

Main active
species

Ref. (year)

h+

[869] (2013)

h+
OH

O2

[870] (2013)

[580] (2014)
+

O2 , h , OH [505] (2015)
[576] (2011)

5.15

O2

MO/0.005 g L1 /100 mL
120 min/93%
2,4-DCP/0.02 g L1 /100 mL 300 min/92%
1
acid orange II/0.05 g L

0.856
4.1

O2

O2 , h

RhB/0.015 g L1 /100 mL

1.41

240 min/90%

phenol/5 ppm/50 mL
1

[871]
(2016)
[872] (2014)

[873] (2014)
[874] (2013)
+

O2

[875]
(2016)
[876] (2015)

0.04

O2 , h+

[877] (2015)

MO/0.02 g L /50 mL
MO/0.01 g L1 /160 mL

70 min/83.3%
240 min/86%

2.05
0.88

O2 , h
O2 , OH

[878] (2016)
[587] (2016)

RhB/10 ppm/100 mL

90 min/87%

2.2

O2 , OH

[879] (2015)

RhB/0.005 g L1 /100 mL
MO/0.01 g L1 /100 mL
DEP/0.01 g L1 /100 mL
MB/0.01 g L1 /100 mL

90 min/91%
2.61
240 min/99%
1440 min/85%
180 min/93%
1.47

[544] (2015)
[880] (2014)

MB/0.01 g L1 /30 mL

40 min/90%

6.88

RhB/0.01 g L1 /50 mL
MO/0.01 g L1 /50 mL
RhB/10 ppm/200 mL

20 min/96%
180 min/95%
120 min/90%

15.2
1.61
1.55

[604]
(2015)
[633] (2016)

MO/0.01 g L1 /100 mL

120 min/100%

MB/0.005 g L1 /100 mL

40 min/100%

[881] (2013)

h+
h+

O2

5.1

O2

[882] (2015)

[688] (2014)
[734] (2014)

ARTICLE IN PRESS

gC3 N4 /Bi2 O2 CO3


gC3 N4 /Bi2 WO6
Bi2 WO6
QDS/g-C3 N4
gC3 N4 /Bi2 WO6
gC3 N4 /Bi2 MoO6
gC3 N4 /Bi2 WO6
gC3 N4 /Bi4 Ti3 O12
HSbO3 /g-C3 N4

Co-catal./optimized
mass ratio

G Model

APSUSC-33598; No. of Pages 52

Photocatalyst

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx


37

Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
http://dx.doi.org/10.1016/j.apsusc.2016.07.030

Table 8 (Continued)

Morphologies and
microstructures

Gas-solid systems for CO2 photoreduction


nanoparticles/nanosheets
Ag3 PO4 /g-C3 N4
g-C3 N4 /Bi2 WO6
m-CeO2 /g-C3 N4
g-C3 N4 /KNbO3
SnO2-x /g-C3 N4

g-C3 N4 /NaNbO3

NaNbO3 nanowires/g-C3 N4
nanosheets
TiO2 nanoparticles/g-C3 N4
nanosheets
worm-like mesostructures

direct thermolysis
in-situ deposition
in situ hydrothermal approach
hard-template route
ultrasonic dispersion followed
by heat treatment method
directly calcining
simple calcination of g-C3 N4
and Sn6 O4 (OH) 4
calcination

2 wt% Pt

S-doped g-C3 N4

layered structures contain


many irregular pore sizes
highly mesoporous

chemical reduction process in


ethylene glycol
simply calcinating thiourea

AgX/g-C3 N4 (X = Cl and
Br)
AgCl/C3 N4

AgCl nanoparticles/C3 N4
nanosheet

GO-g-C3 N4

sandwich-like

RGO/p-C3 N4

sandwich-like

g-C3 N4 /ZnO

a direct Z-scheme mechanism

CO(44) CH3 OH(8.5)


CH4 (2) C2 H5 OH(1.1)
CO(5.19)

[608] (2015)

CO(10.16) CH4 (13.88)

[927] (2016)

CH4 (2.5)

[693] (2015)

0.02/CO2 and H2 O vapor

CO(19.2) CH4(1.4)
CH3 OH(3.1)

[928] (2015)

0.05/CO2 and H2 O
vapor/230 mL
0.1/CO2 and H2 O
vapor/780 mL
0.1/CO2 and H2 O
vapor/2700 mL
/
0.006/CO2 and H2 O
vapor/100 mL

CH4 (6.4)

[929] (2014)

CO(12.25)

[930] (2014)

CO(111) CH4 (15.4)

[931] (2016)

CH3 CHO(8)
CH4 (0.85)

[932] (2015)
[933] (2016)

CO2 and H2 O vapor

CH4 (1.302)

[692] (2015)

0.1 g/CO2 and H2 O


vapor/200 mL
0.01/CO2 and H2 O
vapor/132 mL
0.1/CO2 and H2 O
vapor/200 mL
CO2 and H2 O vapor

CH3 CHO(0.37)

[199] (2015)

CO(39) CH3OH(10)
CH4(4) C2H5OH(1.5)
CH3 OH(0.6)

[536] (2015)

CH4 (1.393)

[934] (2015)

CO(3.44) CH4 (0.2)

[614] (2016)

CH4(0.3) HCHO(0.075)
CH3OH(0.24)

[691] (2014)

/
300 W Xenon short arc
lamp
405 nm < < 723 nm
15 W energy-saving
daylight bulb
300-W simulated solar
Xe arc lamp
500 W Xe lamp

nanoparticles/lamellar

g-C3 N4 Pt

300 W Hg lamp

Pt/g-C3 N4

BiOI/g-C3 N4

300 W Xe lamp,
420 nm
300 W Xe lamp,
420 nm
300 W of Xenon-arc
lamp
300 W Xe lamp,
420 nm
500 W Xe lamp

/
/
0.8%wt Pt

RGO/g-C3 N4

Ref. (year)

hard-template synthesis
solvent evaporation
method

ZnO microcrystals/g-C3 N4
nanosheets
sandwich-Like Hybrid
Nanosheets
BiOI particles/g-C3N4
nanosheets
two-dimensional lamellar
structure and numerous
randomly organized
nanosheets
irregular spheres of
AgX/g-C3N4 nanosheets

Selective products
(activity) [M h1 g1 ]

in situ synthesized by thermal


treatment
simple pyrolysis method

sponge-like structure
B4 C particles/g-C3 N4
nanosheets

g-C3 N4 /ZnO

Mass [g]/systems/Volume
[mL]

300 W xenon arc lamp


> 420 nm
300 W xenon arc lamp

C3 N4 MCF
B4 C/C3 N4

ZnO/g-C3 N4

Light source

1 wt% Pt

a simple impregnation method


a one-step facile calcination
method
electrostatic self-assembly
construction of 2D/2D
in situ syntheized
directly heating and Pt was
deposited on g-C3 N4

sonication-assisted
deposition-precipitation
approach
in situ
depositionprecipitation
approach.
a facile one-pot
impregnationthermal
reduction strategy
a novel combined ultrasonic
dispersion and electrostatic
self-assembly strategy
a one-step facile calcination
method

15 wt% RGO

1 wt% Pt

300 W simulated solar


Xe arc lamp
15 W energy-saving
Daylight bulb
300 W xenon arc lamp
( > 400 nm).
300 W simulated solar
Xe arc lamp

0.1/CO2 and
H2 O vapor/500 mL
0.05/CO2 and
H2 O vapor/500 mL
0.1/CO2 and H2 O vapor

0.1/CO2 and H2 O
vapor/180 mL
0.1/CO2 and H2 O
vapor/200 mL

[926] (2015)

[220] (2015)

500 W Xenon arc lamp,


( > 400 nm)

0.1/CO2 and H2 O vapor

30%AgBr/g-C3 N4
CH4 (1.092)

[935] (2016)

15 W energy-saving
daylight lamp

CO2 and H2 O vapor

CH4 (0.95)

[936] (2016)

15 wt% GO

15 W energy-saving
daylight bulb

CO2 and H2 O vapor

CH4 (5.87)

[702] (2015)

15 wt% rGO

15 W energy-saving
daylight lamp

0.1 g/CO2 and H2 O vapor

CH4 (1.393)

[160] (2015)

300 W simulated solar


Xe arc lamp

0.1 g/CO2 and H2 O


vapor/200 mL

CH3 OH(0.6)

[601] (2015)

ARTICLE IN PRESS

Mo-doped g-C3 N4

g-C3 N4 nanosheets/layered
structure KNbO3
SnO2-x nanoparticles/g-C3N4
sheets are

Cocatalyst

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx

g-C3 N4 -N-TiO2

Bi2 WO6 nanoakes/thin layer


g-C3 N4 nanosheets
mesoporous

Synthesis method

G Model

Material

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Table 9
Summary of the photocatalytic CO2 reduction over g-C3 N4 -based photocatalysts.

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[939] (2016)
250 W lamp,
= 365 nm
nanospheres/aky morphology
CdS/g-C3 N4

polycondensation and
hydrothermal methods

/
a facile one-pot chemical
condensation of urea
dense and stacked particles
and sheets
CNUBAX

300 W Xe lamp,
> 420 nm

0.03/CO2 saturated
solution of CoCl2 ,
2,2-bipyridine,
triethanolamine
0.02/CO2 saturated
methanol solution/20 mL

HCOOH (1352.07)

[938] (2015)

[620] (2014)

Ag/g-C3 N4 + WO3 :
CH3 OH(24.05)
Au/g-C3 N4 + WO3
CH3 OH(34.02)
CO(469)
0.003/CO2 and H2 O
0.5%wt Au,
0.5%wt Ag
WO3 /
g-C3 N4 (P-CW)

planetary mill
photodeposition method

300 W Xe arc lamp


simple thermal condensation
amine functionalization

two-dimensional lamellar and


porous structure with
anomalous shape
highly dispersed WO3
particles/g-C3 N4 particles

ten layers CNNS/the UiO-66


microspheres

amine-functionalized
g-C3 N4

CO(9.9)
/

thermal condensation
of melamine
facile electrostatic
self-assembly method
thin nanosheets

2D hydroxyl-rich C3 N4
nanosheets
UiO-66/10%CNNS

light-emitting diode
(LED), = 435 nm

[227] (2015)
CH4 (0.34)
CH3 OH(0.28)

[708] (2015)

[937] (2015)
CH4 (0.75)

80 mL CO2 saturated water


solution
5 mL CO2 saturated of
solution (MeCN/TEOA
4:1)/330 mL
0.1/CO2 saturated water
solution/200 mL

[697] (2016)
HCOOH(7.8)
0.005/CO2 and MeCN/TEOA
mixture (4:1, v/v) 4 mL

400 W high
pressure Hg lamp with
a NaNO2 solution lter
300 W Xe lamp,
> 420 nm
300 W xenon arclamp,
400 nm< < 800 nm
RuP
adsorption
Suspension systems for CO2 photoreduction
mesoporous structure
RuP/g-C3 N4

Material

Table 9 (Continued)

Morphologies and
microstructures

Synthesis method

Cocatalyst

Light source

Mass [g]/systems/Volume
[mL]

Selective products
(activity) [M h1 g1 ]

Ref. (year)

J. Wen et al. / Applied Surface Science xxx (2016) xxxxxx

39

highest apparent quantum yield of 5.7% at 400 nm for the photocatalytic reduction of CO2 into formic acid under visible-light
irradiation (as shown in Fig. 50) [695]. Surprisingly, the ternary
hybrid of plasmonic Ag nanoparticles and g-C3 N4 /binuclear Ru(II)
complex could achieve a very high turnover number of > 33,000
with a high selectivity of 8799% for HCOOH production, due to the
combination effects of plasmonic Ag and Z-Scheme charge transfer (as shown in Fig. 51) [700]. These are the best values that have
been reported for heterogeneous photocatalysts for CO2 reduction
under visible-light irradiation to date. The present study clearly
highlighted the great potential of complex molecular co-catalyst
on carbon nitride in photocatalytic CO2 reduction under visible
light. Thus, it is expected that the multi coupling of complex molecular co-catalyst, g-C3 N4 and other photosensitizers may provide
exciting opportunities for promising CO2 photoreduction over gC3 N4 -based photocatalysts. In addition, it is also noted from Table 9
that there are few earth-abundant co-catalysts reported to accelerate the CO2 photoreduction over g-C3 N4 -based photocatalysts,
which should be urgently developed in the near future. At this
point, the nano-carbons, such as RGO and CNTs, are highly expected
to coupling with the g-C3 N4 to obtain highly efcient metal-free
g-C3 N4 -based photocatalysts for CO2 photoreduction [934].
Besides co-catalysts, doping and nanostructured heterojunction
were also extensively used to enhance the visible light absorption and photocatalytic CO2 reduction activity of g-C3 N4 -based
photocatalysts. Wang et al. fabricated sulfur-doped g-C3 N4 photocatalysts by employing thiourea as the sulfur precursor for the
reduction of CO2 to CH3 OH [199]. The DFT studies conrmed that
the electrons can be easily excited from the VB to the impurity
state, and then to the CB of sulfur-doped g-C3 N4 owing to the
impurity sulfur doping (as shown in Fig. 52a), which induced additional electrons, resulting in the spin polarization. As the band
gap was narrowed from 2.7 to 2.63 eV, the light absorption was
broadened in the sulfur-doped g-C3 N4 , generating more electrons and holes under the light irradiation. Thus, the CH3 OH yield
(1.12 mol g1 ) was 1.5 times higher than that the unmodied gC3 N4 (0.81 mol g1 ) (as shown in Fig. 52b). In another example,
Yu et al. constructed a binary g-C3 N4 /ZnO photocatalyst with an
intimate contact interface via a one-step facile calcination method
[220]. The results showed that the as-prepared g-C3 N4 /ZnO photocatalytic system exhibited enhanced photocatalytic activity for
CO 2 reduction by a factor of 2.3 compared with pure g-C3 N4 (as
shown in Fig. 53a). The better performances of the g-C3 N4 /ZnO
binary composite photocatalytic system could be well explained
by the direct Z-scheme mechanism rather than the conventional
heterojunction-type mechanism (as shown in Fig. 53b and c), which
was achieved due to the highly efcient ZnO-to-g-C3 N4 electron
transfer occurring at the intimate contact interface between the gC3 N4 phase and ZnO phase. This work highlighted that the rational
construction of direct Z-scheme g-C3 N4 -based photocatalytic system without an electron mediator should be promising strategy for
the applications in the photocatalytic CO2 reduction.
On the other hand, the product selectivity of photocatalytic CO2
reduction should be also a major consideration in designing semiconductor photocatalysts [942]. For example, Liu and coworkers
obtained the g-C3 N4 nanosheets by the thermal delamination of
bulk g-C3 N4 in air. It was shown that g-C3 N4 nanosheets with a band
gap of 2.97 eV yielded the major product of CH4 , whereas bulk gC3 N4 with a smaller band gap of 2.77 eV formed the main product of
CH3 CHO (Fig. 54a) [409]. This elucidated that the nanosheets had a
larger band gap by 0.2 eV, leading to a lower VB edge by 80 meV and
a higher CB edge by 120 meV. Therefore, the nanosheets provided a
larger thermodynamic diving force for the hole and electron transfer by means of a greater difference in energy level between redox
potentials of the reactants and band edges (Fig. 54b). This indirectly led to a larger proportion of long-lived charge carriers for the

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Fig. 49. (a) Photoconversion of CO2 into CH4 , CH3 OH and HCHO over PtX -loaded g-C3 N4 (x, the weight percentage ratios of Pt against g-C3 N4 were 0, 0.25, 0.5, 0.75, 1.0 and
2.0 wt%); (b) Charge separation mechanisms in the Pt/g-C3 N4 systems [691].

of CO2 in order to exclude the possibility of photodissociation of


the organic impurities or even carbon-containing catalysts.
5.4. Photocatalytic selective organic transformations

Fig. 50. Scheme illustration for CO2 reduction using a Ru complex/C3 N4 hybrid
photocatalyst.

Fig. 51. Scheme illustration for Z-Scheme CO2 reduction using a ternary Hybrid of
Ag/g-C3 N4 /Binuclear Ru(II) Complex [700].

nanosheets in contrast to the bulk. As a consequence, the formation


of CH4 was more favorable due to rapid transfer of photoexcited
electrons in the nanosheets to the intermediate species.
However, it is worth mentioning that the current apparent
quantum efciency is still low for the commercial applications.
Thus, there is still ample room to further improve the CO2 photoreduction in g-C3 N4 -based photocatalytic system. Furthermore,
the exact reaction mechanism for the CO2 photoreduction should
be paid more attention. In this regard, various strategies to enhance
the CO2 adsorption of porous absorbents could be employed to
improve the adsorption and activation of CO2 on g-C3 N4 -based
photocatalysts [943945]. Especially, the selectivity of CO2 photoreduction should be deeply investigated for each system. In fact,
it is strongly suggested that all products from the CO2 conversion
requires should be measured, in gas and liquid phase for suspension
systems. To well understand the photocatalytic reaction steps, DFT
can be used to identify the activation state of CO2 . In addition, the
isotopic labeling analysis using 13CO2 as the reactant is nacessary
to conrm the obtained prodcuts stemmed from the photoxation

Recently, the robust metal-free g-C3 N4 -based photocatalysts


have been shown to have great potential for selective organic
transformation under mild conditions, including oxidation of aromatic compounds [395,507,946956], photo catalytic esterication
of benzaldehyde and alcohol [957], oxidative cleavage of the
carboncarbon bond of -hydroxy ketones [958] and allylic oxidation [959]. For example, Wang and coworkers demonstrated
that direct oxidation of benzene to phenol with H2 O2 catalyzed
by porous Fe-g-C3 N4 could be achieved, in both the presence and
absence of visible light irradiation [950]. By taking advantage of
the photocatalytic functions of g-C3 N4 , the yield of the phenol synthesis can be markedly improved. Furthermore, the same research
group demonstrated that the metal-free graphene sheet/g-C3 N4
nanocomposite could achieve the selective photocatalytic oxidation of cyclohexane to cyclohexanone through the superoxide
radical anion ( O2 ) induced from the activation of O2 (as shown
in Fig. 55), highlighting the key roles of O2 -reduction reaction
in the photocatalytic selective organic transformations [244]. In
another report, Zhang et al. [956] revealed that a 38% conversion
of benzene to phenol with 97% selectivity could be achieved using
FeCl3 -modied mesoporous carbon nitride as a visible-light photocatalyst to activate H2 O2 . Li et al. [960] developed a MottSchottky
photocatalyst consisting of mesoporous carbon nitride with Pd
nanoparticles. The efcient electron transfer from the g-C3 N4 to the
Pd resulted in a high photocatalytic activity and selectivity for the
room-temperature C C bond formation by coupling aryl halides
with different coupling partners. More recently, Yin and coworkers
demonstrated that an acid-base bifunctional P-doped g-C3 N4 photocatalysts could achieve the cycloaddition reactions, due to the
synergetic effect of acid (halide anions) and basic sites for ring opening of epoxide and adsorption/activation of CO2 [325]. In future, it
is expected that various kinds of multifunctional g-C3 N4 composite
photocatalysts could be widely used in the selective photocatalytic
organic transformations, which are hardly proceed by traditionary
thermal catalysis. Also, the deep mechanism investigation is highly
desired.
5.5. Photocatalytic disinfection
As a nontoxic, efcient, and stable method, photocatalytic
disinfection has been shown to be superior in comparison with traditional water disinfection methods, including chlorination, ozone,
and ultraviolet (UV), have some disadvantages [659]. Commonly,
the toxic metals in the efcient metal-based photocatalysts for
bacterial inactivation is unfavorable for green water disinfection
[660]. At this point, the robust and non-toxic metal-free g-C3 N4

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Fig. 52. (a) Schematic of band structure of pure g-C3 N4 (left) and S-doped g-C3 N4 (right); (b) Comparison of photocatalytic CH3 OH production over S-doped g-C3 N4 (TCN)
and un-doped g-C3 N4 (MCN) at 3 h under UVvis light irradiation [199].

Fig. 53. Comparison of photocatalytic CH3 OH production rates of cm-ZnO, pure ZnO, G10, and pure g-C3 N4 . Schematic illustration of two different mechanisms for charge
carrier separation: (b) conventional heterojunction-type and (c) direct Z-scheme mechanisms [220].

Fig. 54. (a) Schematic illustration of the photoreduction CO2 to CH3 CHO and CH4 on bulk g-C3 N4 and g-C3 N4 nanosheets. (b) Band structures of g-C3 N4 nanosheets (left) and
bulk g-C3 N4 (right) and the redox potentials of the reactions [409].

Fig. 55. Schematic illustration of the selective oxidation of secondary C H bonds


of cyclohexane through the superoxide radical anion ( O2 ) [244].

seems to be more promising in water disinfection. However, limited


studies have concentrated on the visible-light-induced photocatalytic inactivation of bacteria over g-C3 N4 [450,659,660,961]. For

example, Huang et al. demonstrated that metal-free robust g-C3 N4


photocatalyst exhibit antibacterial activity for the inactivation of
Escherichia coli K-12 (E. coli) under visible light irradiation [961].
Especially, a novel heterojunction related to g-C3 N4 was synthesized via cowrapping the RGO and g-C3 N4 (CN) sheets on -sulfur
(-S8 ) by Wang and his coworkers. The results indicated that
the visible-light-driven photocatalytic activities of this system for
bacterial inactivation was signicantly improved, which will also
change with the shells arrangement evolution of RGO and CN.
The enhanced activities can be ascribed to the electrons or holes
migration in the system as shown in Fig. 56 [660]. In addition,
Zhao et al. indicated that the atomic single layer g-C3 N4 with the
thickness of 0.5 nm exhibited performance of photocatalytic disinfection for inactivation of Escherichia coli, due to low charge transfer
resistance and efcient charge separation [450]. More recently, An
and coworkers demonstrated that the g-C3 N4 /TiO2 hybrid photocatalyst, comprised of micron-sized TiO2 spheres wrapped with
lamellar g-C3 N4 , exhibited signicantly enhanced photocatalytic
activity for the inactivation of Escherichia coli K-12, due to improved
light absorption and the effective charge separation [659].

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Fig. 56. Schematic illustration of the visible-light-driven photocatalytic bacterial inactivation mechanisms of (a) CNRGOS8 ; (b) RGOCNS8 in aerobic condition; (c) CNRGOS8 ;
(d) RGOCNS8 in anaerobic condition [660].

6. Conclusions and future prospects


In summary, this review highlights the advantages, versatile
properties, design strategies and potential application of robust
g-C3 N4 -based composite photocatalysts. Obviously, g-C3 N4 has
proven to be one of the most promising candidates suitable
for designing and fabricating advanced composite photocatalysts
for various applications. Therefore, there is little doubt that the
explosive growth of g-C3 N4 -based composite photocatalysts will
continue to accelerate in the near future. To date, although considerable progress has been achieved in the recent years, there
are still many challenges to rationally fabricate the highly efcient g-C3 N4 -based photocatalysts towards various applications
and deeply understand the underlying enhancement mechanism
of composite photocatalysts by g-C3 N4 . There are still many open
issues and opportunities for further research effort. Accordingly,
more studies are also needed to make full use of the outstanding structural and electronic properties of g-C3 N4 in the composite
photocatalysts.
On the one hand, versatile properties of g-C3 N4 -based photocatalysts are still needed to be explored carefully. Since the highly
effective and stable g-C3 N4 -based photocatalysts with narrowed
band gaps are difcult to obtain, the design and development of
conjugated narrow-band polymer might provide alternative ideas
for boosting the advancements of photocatalysis based on the
organic semiconductors [962968]. Furthermore, the accurate control of surface defects and facile scale preparation methods of
g-C3 N4 nanosheets are highly desired. The advanced electrocatalysts and photoelectrocatalysts based g-C3 N4 should be exploited
as an important research community for extending the applications
of g-C3 N4 -based photocatalysts. Among various design strategies,
the dimensionality tuning, pore texture tailoring, heterojunction
construction (especially for Z-scheme construction), co-catalyst
and nanocarbon loading seem to be more promising in developing
practical g-C3 N4 -based photocatalysts. Typically, Z-scheme construction is more interesting and promising than the traditional

heterojunction. At this point, more investigations should be paid


to this strategy. Absolutely, the developments of earth-abundant
co-catalysts are still a hard task in these photocatalytic elds. The
magical nanocarbons will play the irreplaceable roles in constructing highly efcient g-C3 N4 -based photocatalysts for all the time.
In addition, the applications of g-C3 N4 -based photocatalysts are
mainly focused on the H2 evolution and degradation of pollutants.
However, the photocatalytic CO2 reduction over g-C3 N4 -based
photocatalysts become more and more attractive in the past three
years. The basic nature of the g-C3 N4 surface determines its bright
future in the elds of CO2 reduction. Furthermore, work on the
O2 evolution from the other half-reaction of H2 O splitting should
gain more attention in the near future, which involves in both
the water splitting and CO2 reduction. Additionally, the exact
reaction mechanism, particularly the CO2 reduction using g-C3 N4 based photocatalysts, still remains doubtful and unresolved to date.
The deep studying of reaction pathways is crucial for revealing
the photocatalytic enhancement fundamental and further rationally design the highly efcient g-C3 N4 -based photocatalysts in
the future. Furthermore, some key issues that account for the
high photocatalytic activity, i.e. optical absorption, electronic band
structure, and charge transfer dynamics, should be exhaustively
investigated to gain theoretical insights by means of both computational (rst-principles DFT) and experimental simulations. In terms
of experimental work, reactant adsorption sites, charge transfer
dynamics, and molecular orbitals should also be deeply researched.
The joint efforts by researchers from various elds and countries
must bring one and one exciting time for g-C3 N4 -based photocatalysts.
Acknowledgments
Li would like to thank Industry and Research Collaborative
Innovation Major Projects of Guangzhou (201508020098), NSFC
(20906034) and the State Key Laboratory of Advanced Technology
for Material Synthesis and Processing (Wuhan University of Tech-

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nology) (2015-KF-7) for their support. X. Chen would like to thank


the College of Arts and Sciences, University of MissouriKansas
City and University of Missouri Research Board for their nancial
support.
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Please cite this article in press as: J. Wen, et al., A review on g-C3 N4 -based photocatalysts, Appl. Surf. Sci. (2016),
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