Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50

Contents lists available at ScienceDirect

Journal of Photochemistry and Photobiology C:

Photochemistry Reviews
journal homepage: www.elsevier.com/locate/jphotochemrev

Invited Review

A fantastic graphitic carbon nitride (g-C3 N4 ) material: Electronic

structure, photocatalytic and photoelectronic properties夽
Guoping Dong ∗ , Yuanhao Zhang, Qiwen Pan, Jianrong Qiu ∗
State Key Laboratory of Luminescent Materials and Devices and Institute of Optical Communication Materials, School of Materials Science and Engineering,
South China University of Technology, Guangzhou 510640, China

a r t i c l e i n f o a b s t r a c t

Article history: As an analog of graphite, graphitic carbon nitride (g-C3 N4 ) has been the hotspot in the materials science
Received 15 January 2014 for its unique electronic structure. With medium band gap as well as thermal and chemical stability in
Received in revised form 31 March 2014 ambient environment, it becomes one of the most promising photocatalytic materials. Intensive inves-
Accepted 10 April 2014
tigation has been focus on its photocatalytic performance for various reactions to date. What is more,
Available online 24 April 2014
controllable modulation of its electronic structure via doping or chemical functionalization is available. In
addition, considerable attention has been paid on its photoelectronic application, such as light emitting
Keywords:
device, photocathode, optical sensor, etc. Based on the electronic properties and pathway to modulate its
Graphitic carbon nitride (g-C3 N4 )
Electronic structure
electronic structure, in this review, we highlight the applications of g-C3 N4 ranging from photocatalytic
Photocatalytic to photoelectronic materials.
Luminescence © 2014 Elsevier B.V. All rights reserved.
Photoelectronic materials
Structure and property modulation

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
2. Brief introduction of g-C3 N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3. Electronic structure of g-C3 N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
4. Applications of g-C3 N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.1. g-C3 N4 as catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
4.1.1. As catalyst for Friedel-crafts reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.1.2. As catalyst for oxygen reduction reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
4.1.3. As catalyst for water splitting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
4.1.4. Methods to improve g-C3 N4 photocatalytic efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39
4.2. g-C3 N4 as photoelectronic materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2.1. g-C3 N4 as light emitting devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
4.2.2. g-C3 N4 as photocathodes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.2.3. g-C3 N4 as optical sensors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.2.4. g-C3 N4 applied in cells . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5. Summary and outlook . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48

夽 Dedicated to Prof. J.R. Qiu on his 50th birthday.

∗ Corresponding authors. Tel.: +86 2087114235; fax: +86 2087114204.
E-mail addresses: dgp@scut.edu.cn (G. Dong), qjr@scut.edu.cn (J. Qiu).

http://dx.doi.org/10.1016/j.jphotochemrev.2014.04.002
1389-5567/© 2014 Elsevier B.V. All rights reserved.
34 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Guoping Dong received his PhD degree from Shanghai
Institute of Optics and Fine Mechanics (Chinese Academy
of Sciences) in 2010, where he received the Chinese
Academy of Sciences President Award in 2010. Since then,
he worked in School of Materials Science and Engineer-
ing, South China University of Technology as a research
assistant (2010) and associate professor (2011). He has
coauthored about 80 peer-reviewed papers with around
850 citations. His current research interests are focused on
the design, preparation and photoelectronic properties of
novel photonic materials.
Yuanhao Zhang received his Bachelor degree in Materials
Science and Engineering in 2013, from South China Uni-
versity of Technology. Currently, he is a master student
under the supervision of Dr. Guoping Dong with postgrad-
uate recommendation in School of Materials Science and
Engineering, South China University of Technology. His
current research interests mainly focus on the design and
modulation of novel photocatalysis materials and pho-
tonic materials with tunable photoluminescence.
Qiwen Pan will receive her Bachelor degree in Material
Science and Engineering in Jun. 2014, from South China
University of Technology. Recently, she has earned her
postgraduate recommendation under the supervision of
Dr. Guoping Dong in the School of Material Science and
Engineering, South China University of Technology. And
she will begin her master courses from September 2014.
Her current research interests mainly focus on the design
and fabrication of photonic materials working at new
wavelength.
Jianrong Qiu received his PhD from Okayama University,
Japan in 1992. He worked in Japan Science and Technology
Agency as chief researcher, Cornell University as research
associate fellow and Zhejiang University as professor from
1995 to 2008. He is now CheungKong chair professor of
South China University of Technology. He has authored
more than 300 articles and has around 5200 citations
to his papers. He received Young Scientist Award from
Rare-earth Society of Japan in 1999, Otto-Schott Research
Award from the Ernst Abbe Fund in 2005, and Academic
Award from the Ceramics Society of Japan in 2007. He
serves as associate editor or editor of the Int. J. Appl. Glass
Sci., J. Non-Cryst. Solids, J. Asian Ceram. Soc. and J. Chinese
Ceram. Soc. His current research interests are fabrication of photonic materials and
femtosecond laser interaction with materials.
1. Introduction
Intensive research on carbon nitride materials has been arisen
since the prediction drawn by Liu and Cohen that carbon nitrides
have potential to be the ultrahard materials [1]. With a wealth
of attractive properties such as reliable chemical and thermal
endurance, super hardness, low density, wear resistance, water
resistivity and biocompatibility, carbon nitrides become one of
the most promising materials for surface modification, light emit-
ting device, photocatalysis, etc. [2–4]. Among various analogs,
graphitic carbon nitride (g-C3 N4 ) constructed via tri-s-triazine
units is considered as the most stable allotrope in ambient envi-
ronment.
To date, search suitable new energy resources as well as
pollution-degradation strategies become significant important to
solve the energy crisis and environmental problems. With out-
standing merits including pollution-free and inexhaustible supply,
solar light is believed as the most ideal routines to resolve the
energy crisis and pollution-disposing power. However, low energy
conversion efficiency still restricts its further development. There-
fore, carbon nitrides, an analog of graphite with special electronic
properties, have been a candidate of new photocatalyst in recent
years. Large number of studies has been carried out on the syn-
thesis and application of g-C3 N4 as metal-free catalyst due to its
medium band gap structure [5]. Inspiring works have been reported
to successfully achieve g-C3 N4 as photocatalyst for water-splitting,
opening up a new gate of research on its photocatalytic perfor-
mance [2].
The lone pair of nitrogen endows the tri-s-triazine tectonic
units with special electronic structure [6], so does the 2-D  layer
structure of g-C3 N4 constructed by tri-s-triazine. As an n-type semi-
conductor, the tunable band gap of g-C3 N4 provides a flexible
channel not only to achieve both controllable lowest unoccupied
molecular orbital (LUMO) and highest occupied molecular orbital
(HOMO), which significantly affects the photoelectronic perfor-
mance of g-C3 N4 as a functional layer, but also to simplify the
modification process mainly by elemental doping or heterojunc-
tions structure construction coupling with other semiconductor,
further broadening its application range.
Generally, various morphologies can be obtained flexibly by
template modeling. Among them, mesoporous graphite carbon
nitride (mpg-C3 N4 ) with large internal surface area and intrin-
sic properties is a suitable host material for semiconductor, a
representative application with immobile metal nanoparticles
to constructed heterojunctions semiconductor was summarized
recently [7]. In addition, basing on the optical modification along
with binding with specific guest via functional group ( NH , N ,
NH2 ) exist on the surface of g-C3 N4 , high optical sensitivity can be
obtained benefit from numerous functional group bringing by large
internal surface, which can be applied as optical sensors [8–10].
In this review, we firstly discuss the electronic structure of g-
C3 N4 . Secondly, we aim to summarize the application of g-C3 N4
ranging from photocatalytic to photoelectronic base on its unique
electronic properties. Finally, relationship between photocatalytic
and photoelectronic properties is tried to construct with providing
the pathway to modified electronic structure of g-C3 N4 for enhanc-
ing the performance on its photoelectronic properties.
2. Brief introduction of g-C3 N4
The research of g-C3 N4 originates from the prediction drawn
by Liu and Cohen that carbon nitride could be synthesized to be
ultrahard materials [1]. Unlike conventional organic semiconduc-
tor counterparts, g-C3 N4 exhibits a unique stability, including the
heat endurance and chemical resistance. Thermal gravimetric anal-
ysis (TGA) and thermal gravimetric (TG) on g-C3 N4 indicate that the
as-prepared g-C3 N4 is non-volatile up to as high as 600 ◦ C, and will
be almost completely decomposed until the temperature rises to
700 ◦ C [11–14]. Its excellent chemical resistance emerged in the
work done by Gillan, showing that g-C3 N4 are almost insoluble in
water, ethanol, toluene, diethyl ether and THF [14], which may be
due to the van der Waals between its layers stacking [3]. It is well
known that the flake-like structure of g-C3 N4 is just similar to that
of graphite, and this has been proven by the XRD results in the
previous reports [11,15–18]. In a single layer of g-C3 N4 , both the
triazine and tri-s-triazine ring have been initially considered as its
tectonic units [19–35]. However, the tri-s-triazine later on rede-
fined as the tectonic units due to its superior stability (as shown
in Fig. 1). With development of the study, the opinion becomes a
mainstream in this field of research.
Synthesis strategies to prepare ideal g-C3 N4 have been sum-
marized in 2008 [36]. PVD, CVD, solvothermal method, solid state
reaction and thermal nitridation have been employed in the previ-
ous reports. However, strict conditions were required in the above
protocols. Thermal condensation, a facile new method among the
above strategies, is employed for preparation. The precursors of the
reaction normally adopt nitrogen-rich species, especially melamine
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 1. The schematic diagram of the s-heptazine unit and s-triazine unit structure
[3].
[37–41], which will undergo self-condensation with deammona-
tion process via thermal reaction. Thermogravimetric-differential
scanning calorimetry analysis (TG-DSC) done by Yan et al. (shown
in Fig. 2 [13]) demonstrated that melamine sublimates and con-
denses at 297–390 ◦ C, the following deammonation process and
decomposition of material will occur at higher temperature about
545–630 ◦ C. Intermediate products including melam 8, melem 4e,
and melon 9 will generate during the thermal condesation. A pos-
tulated thermal condensation of melamine 1a is shown in Fig. 3
[37]. Though melam form during the deammonation process of
melamine, it is just as one intermediate products and will finally
transform into melem which have superior thermodynamic stabil-
ity to exist in higher temperature range around 400–500 ◦ C [38–40].
After the deammonition as thermal condensation processing, g-
C3 N4 will be synthesized eventually [36,37,41].
In conclusion, the lone pair of nitrogen and electrons delocal-
ization endows the tri-s-triazine derivatives, for example: g-C3 N4 ,
Fig. 3. Postulated condensation of melamine 1a [37].
35
Fig. 2. TG-DSC thermograms for heating the melamine [13].
with unique electronic structure [6,42,43], which is controllable
due to their tunable band gap. Furthermore, the excellent thermal
and chemical stability make it becomes one of the most promising
semiconductor materials in the exciting research field.
3. Electronic structure of g-C3 N4
The tectonic structure mentioned above endows g-C3 N4 with
desired photoelectric properties [2,36,44,45]. However, few reports
systematically investigate the electronic structure of g-C3 N4 [42].
A model of a-CNx was established, proposing the density state
which demonstrates a relationship between electron transition and
energy band structure involved to electron transition [46]. Lone pair
electron of nitrogen is considered to contribute to the band struc-
ture and form a lone pair (LP) valance band. The mixture of lone
pair state formed by lone pair of nitrogen and the  bonding elec-
tronic states stabilize the lone pair state [6]. Therefore, the lone pair
electron of nitrogen plays an important role in the electronic struc-
ture of carbon nitride. The influence of nitrogen content on optical
properties of carbon nitride thin films investigated by Abd El-kader
et al. also confirmed the same opinion in certain degree [47].
Generally, researches on the nature of electronic structure are
based on various optical and photocatalytic properties. To prove
the band gap modification, doping with negative ions in g-C3 N4
is carried out, yielding positive improvements for both the tun-
able optical properties and the enhanced photocatalytic ability
36 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 4. Electronic structure of polymeric melon. (a) Density-functional-theory band
structure for polymeric melon calculated along the chain (–X direction) and per-
pendicular to the chain (Y– direction). The position of the reduction level for H+ to
H2 is indicated by the dashed blue line and the oxidation potential of H2 O to O2 is
indicated by the red dashed line just above the valence band; (b) the Kohn–Sham
orbitals for the valence band of polymeric melon; (c) the corresponding conduction
band. The carbon atoms are gray, nitrogen atoms are blue and the hydrogen atoms
are white. The isodensity surfaces are drawn for a charge density of 0.01qe Å−3 [2].
[2,4,18,45,48–52]. Because the reduction and oxidation levels are
related to the position of valance and conduction band, density-
functional-theory (DFT) calculations was implemented to look
insight into its electronic structure. The results shown in Fig. 4
indicated the HOMO-LUMO band gap of melon is 2.6 eV, which
decreases from 3.5 eV of melem, and finally decreases to 2.1 eV with
fully formation of condensed g-C3 N4 [2]. The wavefunction investi-
gation indicated that the valence and conduction band are mainly
driven by the nitrogen PZ orbitals and carbon PZ orbitals respec-
tively, in which the photogenerated electrons and holes separate
suggest oxidation and reduction sites for splitting water could take
Fig. 5. (a) Proposed ECL reaction mechanism for g-C3 N4 nanoflake films–coreactant systems; (b) schematic energy level diagram of the PL emission from the carbon nitride
products synthesized via the thermal condensation of melamine [4,45].
place independently in the nitrogen atom and carbon atom. More
interestingly, the redox potential levels of water calculated by ab
initio thermodynamics show that both reduction level and oxida-
tion level of water splitting (shown in Fig. 4) are located in the band
gap of g-C3 N4 [2].
An electrochemiluminescence (ECL) diagram was proposed
(Fig. 5a) to explain the reaction mechanism of g-C3 N4 nanoflake
films (NFF) on the glassy carbon electrode (GCE) in various solu-
tions. Four processes, namely, electron injection (indicated as R1
in Fig. 5a), hole donor production (indicated as R2-R4 in Fig. 5a),
hole injection (indicated as R5-R6 in Fig. 5a), and electron–hole
recombination producing ECL emission (indicated as R7 in Fig. 5a),
are regard as the key for ECL reaction [45]. And another diagram
(Fig. 5b) regarded the tunable photoluminescence (PL) of carbon
nitride was directly caused by continuous narrowing band gap,
causing by the enhancement of g-C3 N4 -conjugated system and
delocalization of electrons [4]. Recently, Wei et al. used the many-
body Green’s function method to investigate electronic and optical
properties of g-C3 N4 . The results indicated that electronic band gap
of the monolayered triazine based g-C3 N4 is 4.24 eV, whereas the
tri-s-triazine based sample is 5.22 eV (direct) and 4.15 eV (indirect),
it was also proposed that the 2p orbital of nitrogen atom together
with the overlap of nitrogen 2p and carbon 2p orbital are mainly
contribute to valence and conduction band of g-C3 N4 , respectively
[42,53,54]. Far away from explicitly for the electronic properties of
g-C3 N4 , therefore, future works are needed to explore more detail
about electronic structure of g-C3 N4 .
4. Applications of g-C3 N4
4.1. g-C3 N4 as catalyst
TiO2 is a traditional catalyst due to its stability and non-toxicity.
However, with relatively wide band gap and charge recombina-
tion, it suffers from low catalyst efficiency in terms of photocatalyst
[55,56]. Compared with TiO2 , g-C3 N4 possesses a proper mid-wide
band gap to absorb visible light efficiently. Besides, its oxidation
and reduction potential is suitable for water splitting. More impor-
tantly, flexibility in modification with metals entrapping to form
active sites with abundant melon moieties is another significant
point for enhance photocatalystic performance. All of these prop-
erties make it become a promising material for photocatalyst. Since
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 6. (a) Stacked g-C3 N4 sheets function as an all-organic solid-statephotocatalyst promoting redox reactions with visible light; (b) chemical interaction of benzene and
defective g-C3 N4 via HOMO–LUMO hybridization of melem and benzene [57].
Wang et al. used g-C3 N4 as photocatalyst to split water for getting
hydrogen successfully [2], intensive researches have been concen-
trated on g-C3 N4 as a catalyst [52,55,57,58,16].
4.1.1. As catalyst for Friedel-crafts reactions
Graphite can induce electrons relocalization in both conduc-
tion and valence band due to its defect such as curvature, edge or
doping atoms [59–61], which act as catalytically active sites in the
oxidative dehydrogenation of ethylbenzene [62,63]. Generally, g-
C3 N4 features almost all electronic properties of graphite, becomes
the most important candidate to complement carbon in materials
application [57]. Therefore, g-C3 N4 is one of the most promising
catalysts for Friedel-crafts reactions. Goettmann et al. have used it
to realize the Friedel-Crafts acylation of benzene. They used hep-
tanes as solvent for the Friedel-Crafts acylation and investigated the
effect on the surface and crystallinity of the employing catalysts, the
results are summarized in Table 1 [5]. In addition, Zhang et al. have
studied the porous g-C3 N4 , whose catalytic properties and chemi-
cally relationship with absorbing and activating benzene is shown
in Fig. 6 [57]. To further explore the chemical interaction between
benzene and defective g-C3 N4 , the HOMO-LUMO hybridization of
melem and benzene was proposed by Goettmann et al. [5]. The
concept is consistent with the results reported by Lebreton and his
coworkers in 1984 who regard the three HOMO feature  symme-
try, whereas HOMO-3 is an antibonding combination of the atomic
orbitals describing the lone pairs of the “aromatic” nitrogen atoms
[64]. It is possible for g-C3 N4 units transfer electron density to ben-
zene through an overlap with these orbitals, resulting in a very
unusual aromatic rings activation as the HOMO consists exclusively
of the PZ orbitals of the heterocyclic nitrogen, which is exactly the
symmetrical to the highest unoccupied -type orbital in the Hückel
model of benzene [36,57]. Subsequently, oxidization of benzene to
phenol was reported under visible light, introducing solid fluori-
nated polymeric carbon nitride (CNF) which employed NH4 F as the
Table 1
Catalytic activity of mpg-C3 N4 in the Friedel–Crafts acylation of benzene [5].a
Catalyst Conversion [%] TOF × 100 [h−1 ]b
mp-C3 N4/0.5 52 3.6
mp-C3 N4/1 80 5.5
mp-C3 N4/1.6 52 3.6
mpg-C3 N4/0.5 90 6.2
Bulk-C3 N4 0 –
Graphite 1 –
a
Reaction conditions: a mixture of benzene (150 mg), hexanoyl chloride (50 mg),
and (C3 N4 ) in heptane (5 g) was stirred at 90 ◦ C for 20 h. The products were analyzed
by gas chromatography
b
Turnover frequency: n (hexanoyl chloride) per n (melem units) per hour.
37
source of fluorine as catalyst [51]. Fig. 7 shows the efficiency of the
introducing catalyst. Compared with pure g-C3 N4 , the performance
of turnover frequency is enhanced significantly via fluorinating.
4.1.2. As catalyst for oxygen reduction reaction
Searching proper materials to absorb solar light in the visi-
ble region efficiently is important for green chemistry. Herein,
charge-transfer catalysis mediated by photosensitizers is one way
to directly convert visible light for chemistry reaction. As men-
tioned above, g-C3 N4 has an appropriate energy band gap to absorb
visible light efficiently. The study of the band position reported by
Zhang et al. shown that the oxidation potential of the conduction
band and reduction level of the valence band local are at about
−1.3 eV and 1.4 eV respectively [65], which meets the demand of
oxygen reduction reaction driven by solar light energy. Su and his
coworkers used g-C3 N4 to realize alcohols oxidation under visi-
ble light [66]. Fig. 8a shows the electrons transfer reactions during
photo-oxidation alcohols via mpg-C3 N4 . Kinetic isotope effect of
the reaction is investigated via monodeuterated benzyl alcohol
(Fig. 8b) to study deeply onto the mechanism details. In addition, Li
et al. utilized nanocomposites of graphene sheet (GS)/polymeric
carbon nitride (GSCN) to activate O2 for selective oxidation of
cyclohexane, which is important for current industrial and fine-
chemical processes [67–69]. Their proposed oxidation mechanism
is shown in Fig. 9. The supposed superoxide radical anion is crit-
ical for the saturated hydrocarbons oxidation system. Herein, the
selective mechanism of the catalytic reaction can be explained as
follows: superoxide radical anion is reduced by excited electrons
from LUMO of g-C3 N4 and it will react with substrates oxidized by
the positive holes of g-C3 N4 . [66,69]. Subsequently, Wang’s group
Fig. 7. Catalytic oxidation of benzene using CNF-x (x indicated the amount of NH4 F,
x = 0.05, 0.1, 0.5, 1.0, 2.0 g). TOF: turnover frequency, n(phenol) per n(melem units)
per hour. Black column, without illumination; red column, illumination with visible
light,  > 420 [51].
38 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50

Fig. 8. (a) Electron transfer reactions with mpg-C3 N4 ; (b) kinetic isotope effect [66].

observed that transition metal could efficiently enhance the pho-

toelectric and catalytic properties of g-C3 N4 , thus conducive to the
selective hydrocarbon oxidation [70].

4.1.3. As catalyst for water splitting

Nowadays, hydrogen is considered as a clean energy to cope
with the energy crisis and environment pollution causing by the
abuse of fossil fuel. The most ideal source of hydrogen is water. Het-
erogeneous photocatalyst with small band gap and suitable band
position plays a key role in utilizing solar energy [71,72,56,73]. To
improve the efficiency for photocatalyst, two ways are summa-
rized: I. Reduce the band gap to adapt the energy of visible light; II.
Separate excitons sufficiently by introducing some defects and local
lattice to reduce the recombination rate of the excited excitons and
holes during the catalytic reaction.
As for g-C3 N4 , the tunable band gap and the properties of elec-
tron localization or anchoring the active sites as the appropriate
microstructure with surface termination as well as defects and
nitrogen atoms makes it become promising materials for water
splitting [3,4,18]. Since the inspiring work done by Wang et al.
utilizing g-C3 N4 to split water for the first time [2], intensive inves-
tigations have concentrated on this field. Wang and his co-workers
improved the catalytic efficiency of water splitting via fluorinat-
ing [51]. Pt/mpg-C3 N4 photocatalyst modified with MgPc dye was
studied on the photocatalytic hydrogen evolution by Takanabe et al.
The results indicate that the performance of photocatalytic activ-
ity depended on amount of loading dye. An appropriate amount
Fig. 9. Schematic representation of the oxidation mechanism [69].
Fig. 10. (a) Mott–Schottky plots and band structure (inset; CB: conduction band, VB:
valence band) of g-C3 N4 () and CNB0.2 (); b) EIS Nyquist plots for CNB samples
(arrow direction: g-C3 N4 ,CNB0.05 , CNB0.1 , CNB0.2 , CNB0.5 , CNB1.0 and CNB2.0 ), with
the inset showing the periodic on/off photocurrent response of g-C3 N4 (solid line)
and CNB0.2 (dotted line) electrodes in 0.2 M Na2 SO4 with −0.2 V bias versus Ag/AgCl
[65].
of dye will enhance the photocatalytic activity, whereas excess
introduction of the dye will be counterproductive. Therefore, the
dye layer on surface of mpg-C3 N4 is crucial for the photocatalytic
reactions. The photocatalytic activity is the highest for charge trans-
fer between monolayer dye to cocatalyst, and increasing thickness
of the layer covers the cocatalyst sites, thus impairs the pho-
tocatalytic activity. [74]. To study the photocatalytic properties
of g-C3 N4 vs. its electronic structure in depth, Zhang et al. car-
ried out the electrochemical analysis of g-C3 N4 and carbon nitride
copolymerization with barbituric acid (CNB). The results includ-
ing Mott–Schottky plots, electrochemical impedance spectroscopy
(EIS) Nyquist plots, and photocurrent response are shown in Fig. 10
[65]. Positive slope of the Mott–Schottky plots indicated that g-
C3 N4 is an n-type semiconductor due to the n-type donor of
nitrogen atoms. Importantly, flat-band potential was also mea-
sured here, and 1.42 and 1.22 V versus Ag/AgCl for g-C3 N4 and
CNB0.2 were proposed, respectively. Thus, both of them encompass
the photocatalytic water reduction potential as depicted inset of
Fig. 10a.
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50 39

Fig. 11. Proposed pathway for the photocatalytic H2 production by. [M(TEOA)2 ]2+ /g-
C3 N4 systems [75].

Recently, a structure which was constructed by the metal-

based catalyst systems combined with g-C3 N4 was designed. It was
found that the nickel-based catalyst system displayed the high-
est catalytic activity and a good performance at H2 evolution. The Fig. 12. Comparison of the XRD spectra of g-C3 N4 with those of Fe/g-C3 N4 hybrids
mechanism of the system is depicted in Fig. 11 [75]. Firstly, the with varying Fe contents. The inset shows the enlarged XRD spectra of 15%- and
electrons populate into g-C3 N4 ’s conduction band (CB) via two 20%-Fe/g-C3 N4 [81].
pathways, one is the sensitization of acriflavine and another is
photo-excitation. And then [MII (TEOA)2 ]2+ (M = Ni, Co) complexes
different transition metals (Fig. 14.). The result indicated that dif-
obtain an electron transferred from the conduction band of g-C3 N4
ferent dopants have different functions. Fe and Cu are potential
and subsequently develop into [MI (TEOA)2 ]+ intermediate, which
to enhance the catalysts efficiency for hydroxylation of benzene
is important for the photocatalytic H2 production. It is a promis-
to phenol with H2 O2 , while Co and Fe are active for the epoxida-
ing approach to improve the catalytic lifetimes of catalyst systems
tion of styrene with O2 [70]. Recently, catalytic performance on
in photochemical H2 production, which combines organic polymer
hydroxylation of benzene by g-C3 N4 doped with different transition
light-harvesting materials with non-precious-metal to construct a
metals was deeply investigated. It is observed that Vanadium-
catalytic system effectively.
doped g-C3 N4 catalyst is the most effective catalyst in the reaction
[58]. Instead of the transition ions impurities, noble metallic ions
4.1.4. Methods to improve g-C3 N4 photocatalytic efficiency
could also act as the catalytic active site [83]. Yan et al. recently
Although the good performance endows g-C3 N4 a bright future
reported that g-C3 N4 doped with noble metallic impurities, like Ag
in the application of catalyst as introduced above, low photocat-
ions, can improve the photocatalytic activity for the methyl orange
alytic efficiency limits its practical application. To date, tremendous
photodegradation [13]. Normally, this is mainly due to the abil-
efforts have been made to improve the efficiency by modify-
ity of electron capture of noble metallic ions, around which the
ing its band gap, morphology and separation of photogenerated
photogenerated electrons aggregate, giving rise to a higher sepa-
electrons and holes, which including doping with metal ions or
ration of photogenerated electrons and holes. Besides the methyl
non-metal ions, designing optimizing heterojunctions and mor-
orange photodegradation, various reactions can achieve utilizing
phological modification.
the noble metal ions doped g-C3 N4 as photocatalyst. The effi-
ciency for NO decomposition is reported increased catalyzed by
4.1.4.1. Enhance photocatalytic properties of g-C3 N4 via doping.
g-C3 N4 with noble metallic or Zn ions doping compared to that of
Impurities doping is an efficient way to tune the electronic struc-
the undoped counterparts [84]. Similarly, doping with Pd is also
ture of solid materials such as TiO2 , silicon and carbon. [76–80].
reported increasing the activity for the direct hydrogenation of
Conventionally, it is also adopted in the carbon nitride materials
by introducing metal or non-metal ions impurities. The participa-
tion of metallic impurities imposes additional binding functions
which lowers the band gap to enhance the absorption of visible
light, endowing the doped system with unique catalytic and photo-
catalytic properties [5,81]. To introduce metal ions into the carbon
nitrides, the corresponding soluble salt mixed with the precursor
of carbon nitride is usually used to dissolve in the deionized water
under stirring to make sure the overall uniform. Metal ions will
be successfully doped into the carbon nitride structure during the
thermal condensation process of precursor.
Despite the doping concentration, the localization of the peaks is
fixed in the XRD patterns (Fig. 12), indicated that the incorporation
of metal ions does not damage the primary structure of g-C3 N4 .
Fe ions tend to stabilize in g-C3 N4 with the form of Fe N bonds.
To further investigate the effect of metal impurities on the elec-
tronic structure of g-C3 N4 , optical absorption spectra are shown
in Fig. 13. The expanded absorption peaks in the wavelength of
visible light are also observed in the Zn-doped samples, which is
due to the d–p repulsion of Zn 3d and N 2p orbitals (as shown Fig. 13. Optical absorption spectra of Fe/g-C3 N4 complexes and g-C3 N4 ; the bandgap
is shifted toward lower energies in the hybrid materials. Arrow direction: g-C3 N4 ,
in the inset of Fig. 13) [81,82]. To summarize the effect of tran-
1%-, 3%-, 5%-, 10%-, 15%-, and 20%-Fe/g-C3 N4 . The inset is the optical spectrum of
sition metals on photocatalytic properties of g-C3 N4 , Ding et al. 10%-Zn/g-C3 N4 , which also demonstrates narrowing of the g-C3 N4 bandgap by the
studied the evolution of electronic structure of g-C3 N4 doped with metal inclusion [81].
40 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50

Fig. 14. (a) UV/vis spectra of g-C3 N4 and M-g-C3 N4 (M = Mn, Fe, Co, Ni, Cu); (b) PL spectra of M-g-C3 N4 (M = Mn, Fe, Co, Ni, Cu) at 400 nm excitation at 298 K [70].

Fig. 15. (a) Phenol hydrogenation over Pd@mpg-C3 N4 ; (b) possible reaction mechanism of phenol over Pd@mpg-C3 N4 [85].

phenol to cyclohexanone [85]. The hydrogenation of phenol was enhancement of photocatalytic performance of non-metallic doped
proposed to be a step-by-step reaction with cyclohexanone as the g-C3 N4 .
“intermediate” (Fig. 15a). Because phenol can form strong O H. . .N
or O H. . . interactions [86], g-C3 N4 can effectively adsorb phenol 4.1.4.2. Enhance photocatalytic properties of g-C3 N4 via design
for its NH and NH2 groups on the surface, therefore, hydrogenation optimizing heterojunctions. Heterojunctions have been applied
reaction can be accelerated as the electronic transfer from g-C3 N4 in semiconductor photoelectronic materials for a long time.
enriched the Pd electron density (Fig. 15b) [85]. Combining with appropriate photocatalyst, several kinds of pho-
Generally, narrower band gap and HOMO levels can be achieved tocatalytic heterojunctions have been developed [94–98]. Both
in conjugated polymers with higher periodic heteroatoms, and for- the anisotype p–n photocatalyticdiodes and isotype heterostruc-
tunately, elements doping is available as the geometry of g-C3 N4 tural photocatalysts including p-GaP/n-TiO2 , p-NiO/n-TiO2 and
[87]. Therefore, doping with non-metallic impurities is another p-GaFe2 O4 /n-PbBi2 Nb1.9 W0.1 O9 or CdS/TiO2 , WO3 /TiO2 , ZnO/TiO2
effective way, which is usually applied to modify materials such and SnO2 /ZnO have been invented [99–107]. The most important
as the graphite, activated carbons, carbon nanotubes and BN nano-
tubes, to improve the photocatalytic properties of g-C3 N4 [88–92].
Compared with the undoped counterpart, boron doped carbon
nitrides exhibits a better catalytic activity for selective oxidation of
toluene and substituted benzylic aromatics [93]. Besides, the activ-
ity for both the photocatalytic hydrogen generation from water/TEA
and the oxidization from benzene to phenol under visible light is
reported improved when g-C3 N4 was fluorinated. It is ascribed to
HOMO and LUMO energy will be changed with incorporation of flu-
orine into g-C3 N4 , giving rise to the enhancement of photocatalytic
performance [51]. The effect of sulfur doped carbon nitride (CNS)
on its photocatalytic properties was also studied. Fig. 16 indicates
that photocatalytic activity for hydrogen evolution was enhanced
by sulfur doping [94]. The first-principles calculation demonstrated
that the band gap of g-C3 N4 reduces via doped with non-metallic
impurities and therefore enhances the absorption of visible light.
Furthermore, it also observed that the contour distribution of g-
C3 N4 HOMO and LUMO increase during vulcanization, leading to
Fig. 16. Wavelength dependence photocurrent generation at CN and CNS-CN-2
the carrier mobility modified and the photogenerated e− /h+ pairs electrodes in 0.2 M Na2 SO4 aqueous solution (containing 10 vol.% triethanolamine)
separate (Fig. 17) [87]. Actually, this may be the nature for the without any bias potential [94].
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50 41

Fig. 17. LUMO (upper red part) and HOMO (lower green part) of doped g-C3 N4 : (a) SN1 , (b) PC1 , (c) Si , (d) Pi . The Fermi level is set to the zero of energy. Gray and blue spheres
represent the C and N atoms, respectively. In addition, yellow and purple spheres represent the S and P atoms (impurities), respectively [87].

effect of this structure is that it can separate photogenerated e− /h+
pairs effectively which is the crucial factor to enhance photocat-
alytic efficiency as mentioned above. Therefore, to improve the
photocatalytic activity of g-C3 N4 , considerable attention has been
focus on the effective separation of the e− /h+ pairs [108–142]. For
example, coupling CN with CNS, the heterostructure and electronic
structure of the CN/CNS heterojunctions studied by TEM as well
as the electron paramagnetic resonance (EPR) spectra are shown
in Fig. 18. The offset of conduction band and valance band in the
two materials makes effective migration for the photogenerated
electrons or holes, therefore enhance the separation of the photo-
generated e− /h+ pairs (schematic illustration was shown in Fig. 18e)
[94].
Generally, carbon nitride materials synthesized by nitrogen rich
precursor via thermal condensation still have the residual NH2
group [13,113–115]. Utilizing amidation reaction to couple other
materials with g-C3 N4 can modify its electronic structure. Take
coupling 1,2,4,5-benzene tetracarboxylic dianhydride (PMDA) with
the NH2 groups in carbon nitride polymer (CNP) (Fig. 19a) as an
example. Fig. 19b shows that coupling with PMDA, the photo-
catalytic performance of the sample is enhanced. It is attributed
to the separation of the photoinduced electrons and holes of
this structure, consistent with the theoretical calculation [116].
In addition, Di et al. have deposed gold nanoparticles on the
surface of g-C3 N4 via deposition-precipitation method to synthe-
size metal-semiconductor junctions. Compared with Pt/g-C3 N4 , Au
nanoparticles possess a better electron capture ability to collect
the photoinduced electrons around, leading to a more effective
separation of the e− /h+ pairs, and therefore performs a higher pho-
tocatalytic activity for H2 evolution from water [117]. Takanabe and
his coworkers integrated magnesium phthalocyanine and meso-
porous g-C3 N4 to explore the photocatalytic evolution hydrogen
42 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 18. (a, b) Typical TEM images of CNS–CN; (c) high-resolution XPS spectra of S2p recorded from CN, CNS–CN and CNS; (d) room temperature EPR spectra of CNS–CN.
Arrow direction in (d): CN, CNS–CN-1, CNS–CN-2, CNS–CN-3, CNS–CN-4; (e) schematic illustration of organic heterojunction formed between CN and CNS. D = donor [94].
of the heterojunction, proposing that the change of photocatalytic
activity is related to charge transfer between magnesium phthalo-
cyanine and mesoporous g-C3 N4 [74].
Recently, a novel heterojunction related to g-C3 N4 was syn-
thesized via cowrapping the reduced graphene oxide (RGO) and
g-C3 N4 (CN) sheets on ␣-sulfur (␣-S8 ) by Wang and his coworkers.
Investigation on the visible-light-driven photocatalytic bacterial
inactivation indicates that photocatalytic activity will be improved
on this system, and the photocatalytic inactivation activities will
Fig. 19. (a) A scheme of the synthesis of the PMDA-coupled CNP (PMCNP); (b)
The photodegradation of methyl orange (20 mg L−1 ) by PMDA, CNP400, CNP450,
CNP520, PMCNP400, PMCNP450 and PMCNP520 samples under visible light
( > 420 nm) irradiation [116].
change with the shells arrangement evolution of RGO and CN,
which is ascribed to the electrons or holes migration in the system
as shown in Fig. 20 [118]. Because of the well-matched overlap-
ping band-structures between g-C3 N4 and CdS, the separation and
transfer of the photogenerated charges is effective, therefore, a
novel heterojunction is expected to construct by coupling the two
materials to overcome the drawback of self-oxidation in pure CdS,
which is caused by the photogenerated holes in the photocatalytic
process [119]. The investigation also indicated that photocatalytic
activity will be enhanced significantly by the effective separation
of photogenerated electrons and holes as shown in Fig. 21. More-
over, C3 N4 –CdS composite materials can exit stably in this work
[120]. In general, most of heterostructures focus on the migra-
tion of photogenerated charges during the composite structure.
The enhancement of photocatalytic activity bring by this struc-
ture is mainly caused by the effective separation of photogenerated
charges.
4.1.4.3. Enhance photocatalytic properties of g-C3 N4 via morphology
modulation. A large surface area is more preferable to the catalyst
because it improves the catalytic efficiency directly. Mesoporous
is a typical morphology to endow the photocatalysts with larger
surface area to enhance the light absorption and charge trans-
fer [120,121]. The morphology can be obtained via nanocasting
technology [3,122–130] or soft templates [131–135]. Owing to con-
siderable concentration draw in this field, carbon nitride materials
with various morphologies have also been synthesized to date,
including mesoporous [5,41,136–140], nanorods [141], nanosheets
[142], hollow vessels [12], nanowires [143] and nanobelts [11].
Surface area of the bulk g-C3 N4 is relative small, normally below
10 m2 g−1 according to Wang’s report [3]. Recently, Niu et al. have
obtained a 306 m2 g−1 high surface area of g-C3 N4 nanosheets via
thermal oxidation etching of bulk g-C3 N4 in air, which is definitely
contribute to its superior photocatalytic activity [142]. The work
done by Goettmann et al. indicates that the carbon nitrides cat-
alytic activity is affected by their morphology directly. In order
to achieve higher photocatalyst efficiency, shape the photocata-
lyst into mosporous to enlarge the surface area is important for
catalyst [5]. As we know, the key to modulate the morphology via
various templates with nanoarchitectures is to spatially confine the
grown of the materials. Ordered or disordered mesoporous carbon
nitride is reported to be synthesized via integrating with templates
by heating ammonium thiocyanate (AT). The resulted morphol-
ogy is obtained after removing template as shown in Fig. 22 [41].
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 20. 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 [118].
Additionally, Li et al. successfully synthesized the condensed car-
bon nitride nanorods (CNRs) by utilizing the anodic alumni oxide
(AAO) nanochannels membrane template to confine the thermal
condensation of cyanamide (Fig. 23). The SEM and XRD (Fig. 24)
results indicated that it is a more condensed and oriented structure,
Fig. 21. Illustrative representation of various photocatalysis systems under visible
light irradiation: (a) C3 N4 ; (b) CdS; (c) C3 N4 –CdS composite [16].
43
which could enhance the performance on photocatalytic activity
[141].
4.2. g-C3 N4 as photoelectronic materials
Incorporating nitrogen into carbon enhances the performance
of carbon materials, including electronic, structural and mechani-
cal properties, especially the improvement of electronic properties
which makes it become a promising material to apply in batter-
ies [144–147], light emitting devices [43,148], fuel cells [149–153],
solar cells, etc. [154,155]. As a member of the carbon nitride mate-
rials, g-C3 N4 also has a bright future in the above application
fields. The sp2 hybridization between carbon and nitrogen forms
-conjugated electronic structure which endows it with excellent
photoelectronic properties [36].
4.2.1. g-C3 N4 as light emitting devices
Currently, intensive investigation focus on the luminescence of
g-C3 N4 [4,18,45,50,156,157] due to its semiconductor properties.
Generally, photoluminescence region is dominated by the optical
band gap and it was demonstrated that the band gap of g-C3 N4 is
tunable with processed temperature. Fig. 25 shows the relation-
ship between the optical band gap and synthesized temperature
which is believes related to tectonic unit of g-C3 N4 [18]. Dong’s
group systematically studied the photoluminescence tunability of
g-C3 N4. By continuous control of the processing temperature, the
resulted emission region of the samples covers from 400 nm to
510 nm, ranging from blue-violet to green as shown in Fig. 26 [4].
A novel energy level mechanism diagram of the carbon nitride
g-C3 N4 nanopowders is proposed based on the two dimensional
-conjugated polymeric network and lone pair of carbon nitride
(Fig. 5b), which concluded the narrowing of band gap was caused
mainly by enhancement of -conjugated polymeric system and
electrons delocalization.
44 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50

Fig. 22. Schematic diagrams for the fabrication of mesoporous graphitic carbon nitride (mpg-CN) and ordered mesoporous graphitic carbon nitride (ompg-CN) from NH4 SCN
using nano-sized SiO2 particles and SBA-15, respectively [41].

Recently, ECL of g-C3 N4 nanoflake films has been reported by

Chen et al. It was found that strong ECL activity with 435 nm
blue light emission can be obtained under the condition of
reductive-oxidative coreactants [45]. Interestingly, ultrathin g-
C3 N4 nanosheets were prepared via exfoliating bulk g-C3 N4 and it
is worth noting that its PL quantum yield can be up to 19.6% [156].
Both the optical properties and ECL activity demonstrates that
g-C3 N4 have a great potential to apply in light emitting device.
Nowadays, commercialized nitrides fluorescent powers with tran-
sition ions or rare earth ions doping are widely used in light
emitting devices. Although their luminescence properties and
quantum efficient are satisfactory, the toxicity of rare earth or tran-
sition metals together with the strict synthesis condition, such as
high temperature and pressure, restricts their broader application.
Therefore, Development of metal free carbon nitride is growing
interest [43,148]. Reyes et al. utilized the amorphous-CNx as light
emitting film to construct a light device, which showed white–blue
electroluminescence emission at room temperature as shown in
Fig. 27 [148]. The investigation of the white light emitting device
shows that the C N bond of amorphous carbon nitride is corre-

Fig. 23. AAO Templating approaches toward CNRs via three steps: (1) Filling the
AAO template (gray) with monomer cyanamide (white); (2) Heating the filled tem-
plates at 600 ◦ C under N2 flow for 4 h; and (3) etching the template to release CNRs
(yellow)a ; a top right: photograph of CNRs in AAO before removing the template;
bottom right: proposed reaction mechanism of water oxidation and reduction [141].

Fig. 25. Values of direct (squares) and indirect bandgaps (triangles) for carbon
nitride powders processed at different temperatures. The solid black lines denote
Fig. 24. (a) SEM images of CNRs; (b) XRD patterns of CNRs and bulk g-C3 N4 [141]. linear fits in the range between 490 and 610 ◦ C, the dotted lines being extrapolations
[18].
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 26. (a) The normalized PL emission spectra of the carbon nitride products synthesized via the thermal condensation of melamine at different temperatures for 2 h
(ex = 280 nm). The inset shows the digital photos of carbon nitride products with (bottom) and without (upper) 254 nm excitation; (b) The Commission Internationale de
L’Eclairage (CIE) chromaticity diagram of the carbon nitride products synthesized at different temperature for 2 h. (1) 350 ◦ C, (2) 400 ◦ C, (3) 450 ◦ C, (4) 500 ◦ C, (5) 550 ◦ C, (6)
600 ◦ C, (7) 650 ◦ C [4].
sponding to the green and blue emission, while red light emission
is caused by the C H bond [43,148,158]. As the emitting region
of g-C3 N4 is consistent with amorphous-CNx emitting region, it is
believed that g-C3 N4 can also be used as the semiconductor layer
for light emitting devices.
4.2.2. g-C3 N4 as photocathodes
Combining photoelectrochemical (PEC) cells and semiconductor
materials to convert solar energy into chemical fuels is a defi-
nitely important way to get sustainable energy to face the current
energy crisis. Consulted that the semiconductor materials usually
employed with n-type semiconductors, therefore, photoanodes
employed with n-type semiconductor such as TiO2 , ZnO, Fe2 O3
and WO3 for PEC water oxidation have been studied intensively.
However, there are few works about employing p-type semicon-
ductor as photocathodes for PEC water reduction, not to mention
employing the polymeric semiconductor. With superior chemical
stability and special electronic structure, g-C3 N4 is a promising
semiconductor for photocathodes. Zhang et al. incorporated the
active carbon sites to obtain a sustainable photocathode which
Exhibits 3 times of higher cathodic PEC activity than that of the
Fig. 27. Emitting light device configuration [148].
45
pure g-C3 N4 [159]. It is believe that the incorporation of carbon can
effectively affect electronic structure of g-C3 N4 through the fol-
lowing routines: (1) the carbon sites can bring an efficient
charge separation indicated by reducing intensity of photoemi-
ssion and this is beneficial for improving charge mobility; (2)
the -conjugated structure is enhanced. Both of the two aspects
contribute to the charge mobility enhancement. In addition, the
nanostructure also has impact on the diffusion path of free carriers,
mass transfer and active sites, and then affect PEC activity. Sponge-
like porosity obtained in this work can provide more active sites.
Different PEC performance between carbon doped and pure g-C3 N4
is depicted in Fig. 28. It is expected that PEC activity can be improved
via balancing electronic structures, change-carrier mobility and
surface area in the future.
Besides directly using as photocathodes, assemble other suit-
able semiconductors with g-C3 N4 to form composite materials
is another valid approach to enhance the materials performance.
With suitable band gap energies, chalcopyrite semiconductors have
been employed as photocathodes recently due to its promising pho-
tovoltaic application. However, during the process of polarizing
the electrode with anodic potential under illumination, irreversible
reactions will occur, leading to the photocathodes degradation and
photocorrosion, which not only affect the lifetime but also limit
solar energy conversion efficiency of photocathodes. Recently, PEC
performance of g-C3 N4 films composite with CuInS2 semiconductor
was studied by Yang et al. [160], and the heterostructure is shown
in Fig. 29. Herein, g-C3 N4 prevent the degradation and photocorro-
sion of CuInS2 , give rise to a stable photocurrent generation, on the
other hand, g-C3 N4 have beneficial effects on charge carrier kinetics
which will modulate the hydrogen redox potential pointing to ben-
eficial band alignment between the film and the substrate, leading
to a +0.15 V shift on onset potential compared to that of the bare
CuInS2 photocathode. Without the nanoscale thickness, however,
g-C3 N4 films will damage the light absorption due to their charge
recombination. Therefore, the thickness of the g-C3 N4 film is the
bottleneck on designing an efficient heterostructured photocath-
ode.
46 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50

Fig. 28. Photoelectrochemical (PEC) properties of carbon nitrides in 0.1 M KCl aqueous solution. (a) The PEC cell configuration and possible charge transfer (the reference
electrode was omitted for clarity). (b) Characteristic photocurrents at g-CN (black) and Alg-5-CN (red) photocathode under a chopped sunlight simulator at a scan rate of
10 mV/s. (c) Transient current response of g-CN (black) and Alg-5-CN (red) at −0.2 V vs Ag/AgCl (sat. KCl) under chopped monochromatic light at 440 nm. (d) Photo action
spectra of g-CN (black), Alg-5-CN (red), and Gel-5-CN (blue) biased at −0.2 V vs Ag/AgCl (sat. KCl) [159].

4.2.3. g-C3 N4 as optical sensors
With the advantage of effective and sensitive detection, as well
as the reliable biocompatibility and adaptability, optical sensing
systems have been drawn considerable attention. Normally, the
optical sensor is molecular receptor with changeable optical
properties depending on their binding specific guests [161,162].
Currently, chromogenic/fluorescent receptors are widely employed
as optical sensor to detect various ions via chromogenic/fluorescent
groups’ interaction with binding guests. The electrons transfer from
the receptors to their binding guest dominates the optical response.

Fig. 29. Schematic of the g-C3 N4 /CuInS2 heterostructure in 0.1 M H2 SO4 solution (pH 1) for conversion of solar energy into chemical energy. The light is incident from above.
The blue part of the solar spectrum is absorbed by the g-C3 N4 film with a band gap of ∼2.7 eV, while the red portion reaches the semiconducting CuInS2 electrode with a
smaller band gap of ∼1.5 eV [160].
 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
Fig. 30. (a) Selective PL response of bulk (gray bar) and c-mpg-C3 N4 (black bar) after
treatment of 1 mm metal ion solutions, and interference of 1 mm of other metal
ions with 1 mm Cu2+ (white bar); (b) PL response of c-mpg-C3 N4 to Cu2+ in the
concentration range 10–100 nm [8].
It is well known that g-C3 N4 is an ideal compound with function-
alities group such as NH2 / NH / N on the surface to endow
strongly absorption of metal ions via chelation or redox reac-
tion. Unlike other sensors with optical receptor hooking on the
porous materials, g-C3 N4 itself is the receptor and thus performs
higher sensitivity. Lee et al. have studied feasibility of detecting
trace amount metal ions in aqueous solution with g-C3 N4 as opti-
cal sensor via observing its photoluminescence quenching effects
[8]. The results shown in Fig. 30 indicated that g-C3 N4 exhibits
excellent sensitivity for Cu2+ . The photoluminescence completely
quenched by Cu2+ with no obvious interference by other metal ions
due to the photogenerated electrons are captured by Cu2+ . More-
over, it can quantitatively describe the degree of quenching by
Stern–Volmer equation: I0 /I = 1 + KSV [Q], where I0 and I represent
Fig. 31. Scheme of a chemosensor for cyanide ions using Cu2+ -c-mpg-C3 N4 [10].
47
the luminescence intensities in the absence and presence of metal
ions, respectively. [Q] is the molar concentration of metal ion and
KSV is the Stern–Volmer constant [8]. Herein, the effect of the con-
centration of Cu2+ on photoluminescence of g-C3 N4 studied by this
equation shows almost a linear relationship.
Subsequently, Barman and his coworker explored g-C3 N4 quan-
tum dots as optical sensor to detect mercuric and iodide ions
via a mechanism terms namely “ON–OFF–ON” [9]. Mercuric can
be detected by quenching photoluminescence of g-C3 N4 quan-
tum dots via formation g-C3 N4 –(Hg)x complex (ON–OFF), and this
complex can act as an optical sensor for iodide as iodide can regen-
eration free g-C3 N4 quantum dots and thus the photoluminescence
recovering (OFF-ON). In addition, cyanide is also detectable by sim-
ilar mechanism via recovering photoluminescence of g-C3 N4 from
Cu2+ -g-C3 N4 complex as shown in Fig. 31 [10]. The basic idea for
optical sensor mentioned above is utilizing the electrons “hole”
formed by guest complex to touch off the quenching of photolu-
minescence.
4.2.4. g-C3 N4 applied in cells
The main challenge for donor-acceptor solar cells is the intri-
cate nanostructure between the donor and acceptor phases, which
is very difficult to obtain and maintain. Traditional fullerenes
acceptor phases do not match the need of LUMO of solar cells.
Therefore, exploring suitable materials to be acceptor phases is
significantly meaningful. With n-type semiconductor properties
and high absorption of visible light, carbon nitride have arose con-
siderable attention in material science. Byers et al. constructed a
bulk heterojunction through composite carbon nitride with poly-
mer phase. The resulted specimen suggests that carbon nitride is a
better alternative compared to fullerenes in solar cells [163]. As for
fuel cells, the efficiency of energy conversion is mainly restricted
by the sluggish kinetics of the cathode oxygen reduction reac-
tion. Generally, besides special catalytic properties for its electronic
properties as previously summarized, g-C3 N4 is also an ideal mate-
rial for entrapping metal ions to form active sites with abundant
melon moieties. And thus it may apply as base materials for fuel
cells via trapping various ions to form active sites to improve the
catalytic performance for fuel cells. Combining graphene with Co-
doped g-C3 N4 as an electrocatalyst, the work done by Liu et al.
found the enhancement oxygen reduction reaction activity, which
is ascribed to Co–Nx active sites and fast charge transfer promoted
by the formation of electron–hole puddle on the interface of the two
composites [164,165]. Therefore, it gives the hope that improving
performance of cathode oxygen reduction reaction in the fuel cells
via employing g-C3 N4 as the catalyst to enhance efficiency of energy
conversion.
5. Summary and outlook
The fundamental study of g-C3 N4 and their application poten-
tial are wide in scope. The special electronic structure of the
material endows their potential applications as catalyst for
Friedel-crafts reactions, oxygen reduction reaction and water split-
ting. At the same time, the way to enhance its photocatalytic
48 G. Dong et al. / Journal of Photochemistry and Photobiology C: Photochemistry Reviews 20 (2014) 33–50
efficiency is also concluded. As for photoelectronic application,
there is no specific application model with g-C3 N4 . However, the
basic photoelectronic properties such as photoluminescence and
photocurrent properties have been investigated and arouse grow-
ing interest.
To date, the modification pathways to enhance g-C3 N4 per-
formance on photocatalyst normally focus on reducing its band
gap to increase light absorption in visible light region or enhanc-
ing the separation of photogenerated electrons and holes thus
reduce the excitons recombination. But, it is worth noting that
oxidation and reduction potential are very important for achiev-
ing photocatalytic process. Therefore, modulating the HOMO and
LUMO with orientation makes both of them encompasses oxi-
dation and reduction potential for the catalytic reaction is an
advisable pathway for future improving g-C3 N4 catalytic efficiency.
What is more, enhancement on photocatalytic activity bringing
by heterojunctions is ascribed to the enhancement on the sepa-
ration of photogenerated electrons and holes. Up to day, to our
best knowledge, there is few work done on this to demonstrate
the concept and thereby constructing relationship between quan-
tum yield and photocatalytic efficiency of g-C3 N4 may uncover
the possible charge transfer during photocatalytic process which
is significant important to guide the modification of the materi-
als.
In addition, base on its tunability photoluminescence and wide
band emission, it is promising to achieve white light emission
via modulating the distribution of emission color by introduc-
ing new photoluminescence center and act as host material to
design energy transfer for excited ions sensitization. Furthermore,
focus on g-C3 N4 quantum dots is also ongoing. A high PEC activ-
ity photocathodes is meaningful to solar energy conversion, and
active impurities doping and composites with other semicon-
ductor with optimized structure are the efficient way to realize
high PEC activity. It is also eagerly anticipated for the activa-
tion mechanism. Though g-C3 N4 possesses fast and easy optical
response when binding with special guests, it still may be interfered
by other guests coexisted in detection environment. Therefore,
constructing a optical sensing system by binding special inter-
mediate guest to g-C3 N4 for acting as unique species detection
sensor is significant important for its biosensor applications due
to the demand for high accurate detection. The most important
role for g-C3 N4 in cells is it may be acted as functional layer for
the solar cells, thereby modulating LUMO to match with holes
injection layer’s work function to reduce electron injection bar-
rier is the key for realization its practical application in this
field.
Acknowledgments
This work was supported by the National Natural Science Foun-
dation of China (51102096, 51072054, 51072060, 51132004), and
the project of Guangzhou Pearl River Science and Technology New
Star.
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