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DOI: 10.1002/asia.

201700540 Focus Review

Solar Water Splitting

Strategies for Efficient Solar Water Splitting Using Carbon Nitride


Yilong Yang+,[a, b] Songcan Wang+,[b] Yongli Li,[a] Jinshu Wang,*[a] and Lianzhou Wang*[b]

Chem. Asian J. 2017, 12, 1421 – 1434 1421 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Abstract: Graphitic carbon nitride (g-C3N4)-based photocata- light the importance of interfacial engineering and nano-
lysts are promising for photocatalytic water splitting to pro- structural control to facilitating charge separation and migra-
duce clean solar fuels due to their low cost, suitable band tion. Other strategies including doping and defect engineer-
structure and excellent photocatalytic performance. This ing are also concisely discussed. Finally, the perspectives on
review focuses on the state-of-the-art progress of the strat- the challenges and future development of g-C3N4-based
egies for modifying g-C3N4-based photocatalysts toward effi- photocatalysts are presented.
cient photocatalytic water splitting. In particular, we high-

1. Introduction With a graphene analogue structure consisting of C and N


atoms, g-C3N4 is considered as the most stable form among
Worldwide energy shortage and environmental issues have various carbon nitrides at ambient conditions, which can be
roused the awareness of energy conservation and environmen- traced back to the prototype of “melon” found by Berzelius
tal protection, stimulating numerous researches on the explo- and Liebig in 1834.[8] Theoretically, there are two models for
ration of renewable and clean energy.[1] Since the first discov- carbon nitride distinguished by different nitrogen-bridged aro-
ery of photoelectrochemical (PEC) water splitting using titani- matic moieties-triazine (C3N3) unit and tri-s-triazine (C6N7) unit
um dioxide (TiO2) as the photoanode,[2] semiconductor-based in the single layer, as shown in Scheme 1. But in reality, it is
photocatalysis has attracted global interest.[3] However, the uti- very challenging to fabricate an ideal carbon nitride crystal
lization of sunlight for TiO2 is restricted in the UV region due due to the incomplete release of NH3. To be consistent in this
to its large band gap energy of & 3.2 eV, resulting in low theo- review, we name all the experimentally obtained imperfect
retical solar-to-hydrogen (STH) conversion efficiency.[4] To effi- carbon nitride materials as g-C3N4. Since its discovery, g-C3N4
ciently use the solar energy, new visible-light-responsive pho- has been demonstrated for various photocatalytic applications
tocatalysts are required.[5] Moreover, to achieve photocatalytic such as H2 evolution,[9] O2 evolution,[10] organic pollutant degra-
water splitting (the change of Gibbs free energy is DG0 = dation,[11] and CO2 reduction.[12] In addition to photocatysis, g-
237.2 kJ mol@1 for splitting one molecule of H2O into H2 and C3N4 and its derivatives are also good candidates for electroca-
1
=2 O2, corresponding to a required potential of 1.23 V per elec- talysis, catalysis, sensing, bioimaging, and templating, etc.
tron transferred), photocatalysts should possess a conduction These new emerging apllications of g-C3N4 are beyond the
band (CB) more negative than 0 V vs. NHE (normal hydrogen scope of this review, which we will not discuss in detail and
electrode at pH 0) and a valence band (VB) more positive than readers may refer to some recent reviews for more informa-
1.23 V vs. NHE.[6] For practical applications, photocatalysts tion.[13] Scheme 2 shows the ideal scheme of water splitting by
should be low-cost with excellent long-term stability. In this g-C3N4. Under light illumination, g-C3N4 photocatalyst absorbs
regard, there are only limited choices of visible light responsive the photons with energy (hn) larger than its band gap energy
photocatalysts. Graphitic carbon nitride (g-C3N4) is one of the of 2.7 eV and the electrons are then excited to the CB, leaving
most promising visible light responsive photocatalysts for holes in the VB.[14] Then, photoexcited electrons and holes are
water splitting due to its suitable band gap (ca. 2.7 eV), appro- transferred to the surfaces of g-C3N4 photocatalyst. Water mol-
priate band positions (CB of ca. @1.1 eV and VB of ca. 1.6 eV, ecules are reduced by the electrons to generate H2 and oxi-
vs. NHE), non-toxicity, abundance, and easy fabrication process, dized by the holes to generate O2. Meanwhile, the photoexcit-
which has attracted worldwide attention since its first report in ed electron-hole pairs are in the energetically unstable states
2009.[7] and thus will recombine within a very short time. Although the
photoexcited electrons and holes of g-C3N4 possess thermody-
namically sufficient potentials for water splitting, three pivotal
[a] Y. Yang,+ Prof. Y. Li, Prof. Dr. J. Wang
issues (i.e. light absorption efficiency, charge separation effi-
Key Laboratory of Advanced Functional Materials
School of Materials Science and Engineering ciency and surface reaction efficiency) still limit the exploration
Beijing University of Technology of efficient g-C3N4-based photocatalysts, which is very difficult
Beijing, 100124 (China) to be obtained from pristine g-C3N4. Therefore, it is highly de-
E-mail: wangjsh@bjut.edu.cn
sirable to modify g-C3N4 for efficient solar-driven water split-
[b] Y. Yang,+ S. Wang,+ Prof. Dr. L. Wang
ting.
Nanomaterials Centre
School of Chemical Engineering and Australian Institute for Bioengineering In recent years, there are a number of review articles discus-
and Nanotechnology sing the synthesis, properties and applications of g-C3N4 based
The University of Queensland materials,[13a, 15] however, a relatively comprehensive and updat-
St Lucia QLD 4072 (Australia)
ed review solely focusing on the strategies of modifying g-
E-mail: l.wang@uq.edu.au
C3N4 for efficient photocatalytic water splitting is still lacking.
[+] These authors contributed equally to this work.
Herein, we focus on refining the recent progress of modifica-
This manuscript is part of a special issue celebrating the 100th anniversary
of the Royal Australian Chemical Institute (RACI). Click here to see the Table tion strategies for g-C3N4 with enhanced solar water splitting
of Contents of the special issue. properties. In particular, interfacial engineering and nanostruc-

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1422 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Scheme 1. Structural models of g-C3N4 arranged by (a) triazine and (b) tri-s-triazine units.

Yilong Yang received his B.S. (2011) from


Jiangxi Science and Technology Normal Uni-
versity and M.S. (2014) from Beijing University
of Technology (BJUT), China. He is a PhD stu-
dent under the supervision of Prof. Jinshu
Wang at Beijing University of Technology,
China. Now, he is a joint PhD student in Prof.
Lianzhou Wang’s group in 2016–2017. His re-
search interests include the design and devel-
opment of 2D g-C3N4-based materials for pho- Scheme 2. Schematic illustration of water splitting by g-C3N4.
tocatalytic/photoelectrochemical energy con-
version.

Songcan Wang received his B.Eng. (2011) and Jinshu Wang is currently Professor and Dean
M.Eng. (2014) from Central South University in College of Materials Science and Engineer-
(CSU), China. He is a current PhD student ing, Beijing University of Technology, China.
under the supervision of Prof. Lianzhou Wang She received her PhD degree from Beijing Uni-
at School of Chemical Engineering, The Uni- versity of Technology in 1999. From 2002 to
versity of Queensland (UQ), Australia. His re- 2004, she was a Postdoctoral Fellow under
search interests are mainly focused on the the supervision of Prof. T. Sato at Tohoku Uni-
design and development of high performance versity, Japan. Wang’s research interests in-
photoanodes for photoelectrochemical energy clude cathode materials, photocatalysis mate-
storage and conversion. rials and solar cells.

Yongli Li received his B. S in 1994 from Lianzhou Wang is Professor at School of


Northwestern University, and M.S. in 1997 Chemical Engineering and Director of Nano-
from Shaanxi University of Science and Tech- materials Centre, the University of Queensland
nology. He obtained his PhD in 2003 from (UQ), Australia. He received his PhD degree
Xi’an Jiaotong University. Currently, he is an from Chinese Academy of Sciences in 1999.
associate professor at College of Materials Sci- Before joining UQ in 2004, he has worked at
ence and Engineering, Beijing University of two national institutes (NIMS and AIST) of
Technology. His research interests include the Japan for five years. Wang’s research interests
synthesis and application of two-dimension include the design and application of semi-
photocatalytic materials for photochemistry conducting nanomaterials in renewable
and efficient solar energy conversion. energy conversion/storage systems, including
photocatalysts.

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1423 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

tural control are efficient to promote charge separation and ing characteristics for solar energy conversion. For example,
transfer, which will be mainly discussed. In addition, other the water oxidation reaction is the key challenge for overall
strategies such as doping and defect engineering will also be water splitting because it is a four-electron process. If water is
briefly introduced. The challenges and future development of first oxidized to H2O2 and H2 via a two-electron process, fol-
g-C3N4-based photocatalysts for water splitting will be dis- lowed by another two-electron process for decomposing H2O2
cussed in the conclusion section. We hope to provide the to O2 and H2O, higher efficiency can be achieved.[17] CDs are
state-of-the-art information for inspiring the design of efficient excellent catalyst for H2O2 decomposition. Therefore, a CDs-g-
g-C3N4-based photocatalysts for solar fuel generation. C3N4 (CDCN) nanocomposite showed impressive performance
for overall water splitting under visible light illumination
(Figure 1). The apparent quantum efficiencies (AQEs) in the
2. Strategies for modifying carbon nitride
wavelengths of 420 : 20 nm, 580 : 15 nm, and 600 : 10 nm
Thermodynamically, g-C3N4 possesses the ability for overall were 16 %, 6.29 % and 4.42 %, respectively, with a STH efficien-
water splitting. With a band gap of & 2.7 eV, the theoretical cy up to 2.0 %. In addition, graphene oxide quantum dots/g-
STH efficiency is ca. 6 % under AM 1.5 G illumination.[16] Howev- C3N4 also showed enhanced photocatalytic activity.[20]
er, the highest reported STH efficiency for g-C3N4 based photo-
catalyst is & 2 % with some debates,[17] indicating that g-C3N4
suffers severe charge recombination. Therefore, effectively sup-
pressing charge recombination is the key to further improve
its STH efficiency. Generally, interfacial conditions, nanostruc-
tures, and crystallinity strongly affect charge separation of
a semiconductor. Proper interfacial conditions can promote
charge separation and accelerate surface kinetics. Likewise,
suitable nanostructure is beneficial for the migration of photo-
excited electrons and holes to the surface for water splitting
reactions. On the other hand, crystal defects usually play a role
in trapping charge carriers and serve as recombination centers.
Thus, higher crystallinity usually exhibits increased photocata-
lytic activity. In this section, we will mainly discuss the mecha-
nism and recent progress of interfacial engineering and nano-
structural control for modifying g-C3N4-based photocatalysts
with enhanced photocatalytic water splitting performance.
Moreover, other emerging strategies in recent years will also
be concisely introduced at the end of this section.

2.1. Interfacial engineering


Amongst the available strategies, modifying the interfaces of
a semiconductor by introducing other materials such as quan- Figure 1. (A) TEM image of CDots-C3N4. (B) A high magnification TEM image
tum dots, cocatalysts, and hetero/homo semiconductors, etc., of the CDots-C3N4 in red region of (A). (C) HRTEM image of a single CDot in
has attracted much attention due to its great potential in sepa- red region of (B). (D) Corresponding FFT pattern of the crystallite in (C).
(E) Cycling H2 and O2 generation from water at l > 420 nm by CDots-C3N4
rating photoexcited charges as well as improving the photoca- (1.6 V 10@5). (F) QE of different concentrations of CDots in CDots-C3N4 compo-
talytic activities.[18] Based on the species introduced to com- sites. The inset shows a magnified curve of the low concentrations of CDots
bine with g-C3N4, the state-of-the-art interfacial engineering for in the red region of (F). Reprinted with permission from ref. [17]. Copyright
g-C3N4 can be generally divided into five types: carbon/g-C3N4 T 2015, American Association for the Advancement of Science.

junction, cocatalyst/g-C3N4 junction, polymer/g-C3N4 junction,


semiconductor/g-C3N4 junction, g-C3N4/g-C3N4 isotype junction.
All of the classification mentioned above will be discussed in Due to the similar aromatic structure, carbon based materi-
detail in the following sections. als such as carbon ring, graphene, carbon nanotube (CNT) and
carbon framework (CFW) can be seamlessly connected with g-
C3N4 to form C-CN junctions via continuous p-conjugated
2.1.1. Carbon/g-C3N4 junction
bond, which can enhance the electron transfer efficiency,
With the p-conjugated structures, carbonaceous nanomaterials reduce charge recombination, resulting in improved photoca-
exhibit many unique optical and electric properties, which has talytic activity.[21] For example, carbon was in situ grown with
attracted great attention as effective supports to couple with an interconnected framework of mesoporous g-C3N4 nanofib-
photocatalytic nanomaterials to retard the recombination of ers, which exhibited an extremely high H2-evolution rate of
the photogenerated electron-hole pairs.[19] Loading carbon 16 885 mmol h@1 g@1, and a remarkable AQE of 14.3 % at 420 nm
dots (CDs) onto the exterior surfaces of g-C3N4 shows fascinat- without any cocatalysts.[21a] Likewise, g-C3N4 modified by CFW

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1424 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

was constructed through a facile thermal condensation proc- prove light harvesting due to their localize surface plasmon
ess.[21b] The obtained CFW/g-C3N4 composites exhibited obvi- resonance (LSPR) effect.[18] For instance, silver quantum cluster
ously enhanced photocatalytic H2 production rates compared (Ag9) was grafted on the surface of g-C3N4 for photocatalytic
to pure g-C3N4 under visible light irradiation. Carbonaceous hydrogen generation, which exibited enhanced visible light ab-
nanomaterials with p-conjugative structures can be combined sorption.[22a] Metal-to-ligand charge transfer (MLCT) between
with g-C3N4 due to their special structures and unique electron Pt2 + and g-C3N4 played an important role in photocatalysis, as
conducting ability.[21c] In particular, a two-dimensional carbon demonstrated in Figure 2.[22b] The microscopic frame structure
ring (Cring)/g-C3N4 in-plane heterostructure promoted the pho- of g-C3N4 as a polymeric ligand provided N coordination sites
toexcited electrons transporting through the confinement in- filled with six lone-pair electrons, supplying ideal sites for the
plane p-conjugated electric field, resulting in highly efficient inclusion of Pt cation, which exhibited dramatic photocatalytic
overall water splitting.[21e] As a result, the in-plane heterostruc- performance under full-light spectrum illumination. Due to
tural (Cring)-g-C3N4 nanosheets could efficiently split pure water their rare and expensive nature, the utilization of noble metal
under light irradiation with a H2 production rate up to should be as little as possible. In this regard, Li et al. reported
371 mmol g@1 h@1 and a notable AQE of 5 % at 420 nm. In addi- single-atom Pt as a cocatalyst for photocatalytic H2 evolu-
tion, CNT/g-C3N4 composite also showed enhanced H2 evolu- tion.[22c] The isolated single Pt atoms were anchored on g-C3N4
tion.[21d] (Pt-CN) via a simple liquid-phase reaction leading to high dis-
persion and stability, which achieved the maximum utilization
of Pt atoms and remarkably enhanced the photocatalytic H2
2.1.2. Cocatalyst/g-C3N4 junction
evolution activity. As a result, nearly 50 times higher photoca-
Cocatalysts can greatly promote surface kinetics, decrease over talytic activity was observed compared to bare g-C3N4.
potentials of H2/O2 evolution, accelerate the separation of pho- Although noble metals are excellent HECs for water splitting,
togenerated electron/hole pairs and strengthen the stability of the utilization of noble metals is not suitable for scale-up appli-
semiconductors. Loading cocatalyst on the surface of g-C3N4 cations because of the high cost. During the past decades,
can highly improve the hydrogen evolution reaction (HER) and earth abundant HECs such as Ni, MoS2 and WS2 etc. have been
oxygen evolution reaction (OER) for water splitting. Based on developed, which also showed excellent photocatalytic water
the different effect on the reaction, cocatalyst can be divided splitting performance.[23] For example, loading Ni0 on g-C3N4
into hydrogen evolution cocatalyst (HEC) for water reduction exhibited high photocatalytic activity and stability.[23a] With the
and oxygen evolution cocatalyst (OEC) for water oxidation. optimized amount of Ni (7.40 wt %), the photocatalytic H2 pro-
These two kinds of junction are marked as HEC/CN junction duction rate of Ni/g-C3N4 was increased to 4318 mmol g@1 h@1
and OEC/CN junction, respectively. and no noticeable decrease was observed during 4 runs for
Noble metals such as Ag, Au, Pd and Pt have been consid- 48 h in an aqueous triethanolamine solution. Even under natu-
ered as fascinating HECs for H2 evolution.[22] In addition to their ral sunlight illumination, the Ni/g-C3N4 composite still exhibited
function as HECs, noble metal nanoparticles (NPs) can also im- a H2 generation rate of 4000 mmol g@1 h@1.

Figure 2. (a) Structural illustration for the Pt2 + linking with g-C3N4. (b) k3-weighted Fourier-transform Pt L3-edge EXAFS spectrum of g-C3N4-Pt2 + (0.18 wt %) in
the reference of Pt foil. (c) Metal-to-ligand charge transfer (MLCT) progress: from the state of Pt2 + -induced hybrid HOMO to the LUMO of g-C3N4-Pt2 + . (d) H2
generation rates with g-C3N4-Pt2 + (0.18 wt %) under l > 400 nm, 400 nm < l < 470 nm and l > 470 nm. (e) Cycling photocatalytic H2 generation of g-C3N4-Pt2 +
(0.18 wt %) under l > 400 nm. Reprinted with permission from ref. [22b]. Copyright T 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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Focus Review

Due to the sluggish kinetics, OER is much more challenging op earth-abundant cocatalysts with competitive performance
compared to HER. Thus, exploring high performance OECs is with noble metals or noble metal oxides.
also important for efficient water splitting. Generally, noble
metal oxides such as RuO2 and IrO2 are excellent OECs for pho-
2.1.3. Polymer/g-C3N4 junction
tocatalytic oxygen evolution.[24] Similar to HECs, low-cost OECs
including cobalt compounds (e.g. Co@Pi, Co(OH)2, CoOx, As conducting polymers exhibit excellent electrical, chemical
Co3O4), NiFe, and MnO2 have been developed to replace noble and optical properties, some reprehensive polymers have been
metal oxides.[25] As one of the most effective OECs, Co-Pi has employed to modify g-C3N4 with enhanced photocatalytic acti-
been used to improve the photocatalytic performance of g- vity.[23d, 27] For instance, a new type of g-C3N4-based polymer
C3N4, with the corresponding H2 and O2 evolution rates that composite for enhanced photocatalytic H2 evolution was re-
are 9.6 and 6.8 times higher than the unmodified g-C3N4, re- ported, as shown in Figure 3.[27b] g-C3N4 photocatalyst was
spectively.[25a] Similarly, Co3O4/g-C3N4 hybrid photocatalyst ach- modified by co-loading poly(3,4-ethylenedioxythiophene)
ieved an AQE of 1.1 % at 420 nm for water oxidation.[25c] In ad- (PEDOT) as a hole transport pathway and Pt as an electron
dition, ultrafine cobalt species,[25d] and NiFe/N-doped graphe- trap. The as-prepared C3N4-PEDOT-Pt composites showed dras-
ne[25e] are also efficient OECs for g-C3N4. tically enhanced activity for visible light driven H2 production
Furthermore, the ternary system of cocatalyst and g-C3N4- compared to C3N4-PEDOT and C3N4-Pt, possibly due to the spa-
based composites has also been developed for H2 evolution tial separation of the reduction and oxidation reaction sites.
and even for overall water splitting.[26] CdS nanorods/g-C3N4
heterojunctions loaded with NiS cocatalyst were fabricated via
2.1.4. Semiconductor/g-C3N4 junction
an in situ hydrothermal method. When loading 9 % of NiS, the
ternary hybrid materials showed the best H2-production rate of Introducing another semiconductor to g-C3N4 can induce built-
2563 mmol h@1 g@1, which was 1582 times higher than that of in electrical potential in the interfaces, which drives the separa-
the pristine g-C3N4. The enhanced photocatalytic activity was tion of photoexcited electrons and holes. Based on the differ-
ascribed to the synergistic effects of NiS cocatalyst and the for- ent components modifying g-C3N4, various semiconductor
mation of intimate heterojunctions between 1D CdS nanorods junctions including organic metal molecule/CN junction,[28]
and 2D g-C3N4 nanosheets, accelerating charge transfer and polyoxometallate/CN junction,[29] metal oxide/CN junction[30]
separation, and promoting the surface H2-evolution kinetics. and sulphides/CN junction[31] will be discussed in detail in the
Most of the reported g-C3N4 based photocatalysts only use following section.
HECs or OECs to promote HER or OER half reactions. Loading A heterostructure of m-oxo dimeric iron(III) porphyrin
both HECs and OECs as dual cocatalysts is important for overall [(FeTPP)2O]/g-C3N4 formed with interactions between the p–p
water splitting. However, it is challenging to reasonably control and the Fe-amine was fabricated.[28] It was demonstrated that
the balance between HECs and OECs in one semiconductor. (FeTPP)2O not only acted as a photosensitizer, but also played
For H2 production, Pt is still the most commonly used HEC in the role in prohibiting charge recombination. The obtained
g-C3N4 based photocatalysts. Therefore, it is necessary to devel- pure organic g-C3N4/(FeTPP)2O heterostructure exhibited dra-

Figure 3. (a) Schematic illustration of the preparation process of the C3N4-PEDOT-Pt composite and the proposed photocatalytic reaction. (b) H2 evolution
rates of a. pure g-C3N4, C3N4 with PEDOT loading of b. 0.5 wt %, c. 1 wt %, d. 2 wt %, and e. 5 wt % and (f) C3N4-2 wt % PEDOT without Pt. (c) The cycling of H2
evolution of C3N4-PEDOT-2 wt %. Reprinted with permission from ref. [27b]. Copyright T 2015 The Royal Society of Chemistry.

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1426 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Figure 4. (a) Schematic illustration of possible formation mechanism of g-C3N4/InVO4. (b) Photocatalytic H2 evolution under l > 420 nm for different samples.
(c) Schematic illustration of band alignment of g-C3N4/InVO4 composites under visible light irradiation. Reprinted with permission from ref. [29a]. Copyright T
2015, American Chemical Society.

maticaly enhanced photocatalytic H2 production under solar oxide/CN junctions such as Ag2O/CN,[30a] CeO2/CN,[30b] Cu2O/
light illumination without any cocatalysts, compared to pure g- CN,[30c] TiO2/CN,[30d] and TiO2/In2O3/CN ternary heterojunction[30e]
C3N4, (FeTPP)2O and mixed g-C3N4 and/or (FeTPP)2O. In situ hy- have been fully studied. For instance, Ag2O/g-C3N4 showed effi-
drothermally grown InVO4 nanoparticles onto the surface of g- cient photocatalytic H2 evolution under visible light irradiation,
C3N4 exbhited enhanced photocatalytic H2 production (Fig- which was about 274 times higher than that of pure g-C3N4,
ure 4).[29a] The obtained g-C3N4/InVO4 (with a mass ratio of and was even much better than that of Pt/g-C3N4.[30a] More im-
80:20) nanocomposites achieved effective separation of portantly, Ag2O/g-C3N4 also demonstrated relatively good pho-
charge-hole pairs and stronger reducing power, which pos- tocatalytic H2 evolution even after 16 h of recycling measure-
sessed the maximum photocatalytic activity of ment. In addition, introducing other semiconductor into the g-
212 mmol h@1 g@1 for H2 evolution, corresponding to an AQE of C3N4-based heterojunction is also effective to further improve
4.9 % at 420 nm. In addition, vanadate (AgVO3, BiVO4, InVO4 the photocatalytic activity. For example, the H2 generation rate
and CuV2O6) QDs/g-C3N4 heterojunctions, g-C3N4/Ca2Nb2TaO10 of novel TiO2-In2O3@g-C3N4 ternary system was increased by
and g-C3N4/(Co, Ni)Fe2O4 heterojunctions also showed en- 48 times than that of pure g-C3N4.[30e] The interfacial transfer of
hanced H2 evolution under visible light irradiation.[9c, 29b,c] charge carriers among TiO2, In2O3 and g-C3N4 contributed to ef-
Metal oxide photocatalysts are one of the most important fective charge separation and enhanced activities. Further-
materials in the photocatalytic field. The representative metal more, a special Z-Scheme junction can be directly used in

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Focus Review

overall water splitting. For example, a one-step hydrothermal creased from 2.75 to 2.00 eV (Figure 5).[33a] Cyano terminal C/N
process was developed to synthesize TiO2/g-C3N4 heterojunc- groups, acting as electron acceptors, were introduced into the
tions.[30f] With the redox mediators of I@/IO3@ , and Ni(OH)2/WO3 DCN sheet edge, which endowed the DCN with both n-type
loaded as the oxygen evolution photocatalysts, Z-scheme over- and p-type characteristics, generating p-n homojunctions. This
all water splitting can be achieved. isotype junction structure was demonstrated to be highly effi-
Due to the layer structure and appropriate band gap, sul- cient in charge transfer and separation and resulted in a 5-fold
fides have attracted much interest in photocatalysis. Two-di- enhanced photocatalytic H2 evolution activity. In addition,
mensional CaIn2S4/g-C3N4 heterojunction with intimate interfa- other g-C3N4/g-C3N4 junctions such as tubular g-C3N4 isotype
cial contact were synthesized by a facile two-step method, heterojunction (TCNH),[33b] roll-like g-C3N4 photocatalyst,[33c] and
which exhibited significantly enhanced H2 evolution under visi- g-C3N4/S-mediated g-C3N4 (CN/CNS) isotype heterojunctions
ble light irradiation.[31a] It was believed that the enhanced pho- have also been reported.[33d]
tocatalytic performance mainly stemmed from the enhanced Based on the discussion above, we can briefly summarize
charge separation efficiency between CaIn2S4 and g-C3N4. the obvious advantages of the g-C3N4-based heterojunctions
for water splitting, including more efficient charge transfer and
separation, longer time of charge carriers and spatial separa-
2.1.5. g-C3N4/g-C3N4 isotype junction
tion of the reduction and oxidation reactions. Nevertheless,
To promote charge separation, an effective method mentioned the disadvantages cannot be ignored. For instance, the redox
above is to combine g-C3N4 with guest semiconductors to con- abilities of the photoexcited electrons and holes will normally
struct heterojunctions, which can induce opposite transfer of become weaker, some range of light absorption in the hetero-
photoexcited electrons and holes.[32] Due to such configura- junctions is often blocked, the ratio of different components
tions built from two distinct semiconductors, an efficient heter- cannot be accurately controlled, and the interfacial charge
ojunction is not only determined by their energy band match- transfer is challenging. Thus, further development of hetero-
es but also affected significantly by their crystal structures, sur- junctions should focus on solving the above mentioned issues
face/interface properties and other characteristics, which towards better photocatalytic efficiency.
makes it difficult for practical applications. In contrast, homo-
junction photocatalysts composed of the same semiconductor
2.2. Nanostructural control
materials are much favorable for charge transfer across the in-
terface and facilitating charge separation. In this regard, g- With large surface area and small particle size, nanostructured
C3N4-based organic isotype junction photocatalysts have also materials can provide more sites for the redox reactions, in-
been developed.[33] For instance, defect-modified g-C3N4 (DCN) crease absorption coefficient, decrease the diffusing distance
photocatalysts was prepared via a NaBH4 treatment, which of electrons and holes to the reaction sites, and reduce light
showed much extended light absorption with band gaps de- reflection, etc.[34] Moreover, different nanostructures also show

Figure 5. (a–b) SEM images of CN and DCN-350; with insets showing corresponding digital graphs of (a–b), respectively. (c) Schematic illustration of the prep-
aration process of DCN. (d) Schematic illustration of charge transfer in the p-n homojunction of DCN. (e) Cycling of H2 evolution for pristine CN and DCN-200
under visible-light irradiation. Reprinted with permission from ref. [33a]. Copyright T 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1428 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

various optical, physical and chemical properties. In recent de- & 2 nm thickness, large aspect ratios, high surface area, and
cades, the structure–activity relationship of g-C3N4 materials stoichiometric N/C ratio not only provided abundant reactive
has aslo been explored. According to the obtained nanostruc- sites for H2 evolution, but also promoted charge separation/
tures, nanostructural control can be primary classified to 1D transfer. Consequently, the g-C3N4 nanosheets exhibited very
rod-like nanostructures, 2D sheet-like nanostructures, and 3D good photocatalytic performance for H2 evolution under visi-
sphere-like nanostructures based on their dimensional struc- ble light illumination. Crystalline 2D g-C3N4 nanosheets were
tures. obtained by a one-step liquid exfoliation of the layered bulk
material in water.[44c] The obtained nanosheets with 1–2 nm in
height formed chemically and colloidally stable suspensions
2.2.1. 1D Rod-like nanostructure
under both basic and acidic conditions and showed significant-
Compared to bulk materials, 1D nanostructures with large sur- ly enhanced visible-light driven photocatalytic activity toward
face area and high length/diameter ratio can shorten the H2 evolution compared to the bulk counterpart, which was as-
charge diffusion length and increase the interaction with light cribed to the crucial role of morphology and surface area on
and electrolyte, resulting in fast charge carrier transport and the photocatalytic performance of g-C3N4 materials. Li et al.
enhanced light harvesting.[35] For example, nanoporous 1D g- prepared macroscopic foam-like holey ultrathin g-C3N4 nano-
C3N4 microrods showed 26 times higher photocatalytic H2 evo- sheets (CNHS) fulfilled with micro-, meso-, and macropores via
lution performance (34 mmol g@1) than its bulk counterpart long-time heating bulk g-C3N4 under air atmosphere (Fig-
(1.26 mmol g@1).[35] Furthermore, the photocurrent stability of ure 6).[44d] The CNHS exhibited superior performance in H2 evo-
this 1D nanoporous g-C3N4 over 24 h indicated excellent pho-
tocorrosion resistance. The improved photocatalytic activities
were attributed to prolonged carrier lifetime due to its quan-
tum confinement effect, promoting separation and migration
of charge carriers, as well as the increased reaction sites all
over the microrods. The bottom-up fabrication of g-C3N4 nano-
rods was realized through the direct infrared heating of di-
cyandiamide with no extra templates or organics, which also
showed enhanced photocatalytic activity.[36] Phosphorus-doped
hexagonal tubular carbon nitride (P-TCN) with the layered
stacking structure was obtained from a hexagonal rod-like
single crystal supramolecular precursor prepared by self-assem-
bly of melamine with cyanuric acid under phosphorous acid-
assisted hydrothermal conditions.[37] The tubular structure led
to enhancement of light scattering and active sites. Thus, the
P-TCN exhibited a high H2 evolution rate of 67 mmol h@1 (0.1 g
catalyst, l > 420 nm) in the presence of sacrificial agents, and
an AQE of 5.68 % at 420 nm. With anodic alumni oxide (AAO) Figure 6. (a) Schematic illustration of the preparation of foam-like holey ul-
as templates, 1D g-C3N4 was obtained with increased crystallin- trathin g-C3N4 nanosheets. (b) H2 evolution rate of different samples. (c) Cy-
ity, extended domain size and lowered HOMO position.[38] Simi- cling of H2 evolution for CNHS. Reprinted with permission from ref. [44d].
Copyright T 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
larly, g-C3N4 nanorods (CNRs) were also facilely fabricated by
using chiral mesostructured silica nanorods as template.[22d, 39]
lution which was attributed to the holey 2D ultrathin structure
and the in-plane holes of g-C3N4 nanosheets. These features
2.2.2. 2D sheet-like nanostructure
enlarged specific surface area, exposed more new edges and
In addition to large surface area, 2D nanosheets possess ex- catalytic active sites, improved the electron transport ability,
tremely thin thickness and numerous surface groups for an- and were also beneficial for the rapid cross-plane diffusion of
choring cocatalysts or other materials, which makes this photogenerated carriers.
unique structures promising for fabricating functional hybrid
materials.[40] Since the discovery of 2D monolayer graphene,
2.2.3. 3D Sphere-like nanostructure
a number of 2D photocatalysts including graphene oxide,[41]
MoS2,[42] phosphorus,[43] etc. have been developed. Compared 3D sphere-like nanostructures also exhibit high accessible sur-
to the above mentioned 2D photocatalysts, 2D g-C3N4 exhibits face area and can serve as a host scaffold for designing multi-
tremendous advantages such as good chemical stability, layer shell structures, which inhibits the restacking and aggre-
unique surface properties, and proper band edge positions for gation of the subunits, increases the light scattering, and pro-
water splitting, which has attracted increasing attention in motes surface dependent reactions.[45] Thus, creating 3D
recent years.[44] For instance, free-standing g-C3N4 nanosheets sphere-like nanostructure on g-C3N4 is considered as a promis-
were synthesized by liquid phase exfoliation using isopropanol ing approach to promote directional charge separation to-
(IPA) as the solvent.[44a] The resulting g-C3N4 nanosheets with wards high-performance photocatalysts.[46] For example, the

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1429 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Figure 7. (a) Schematic illustration of the synthesis of HCNS and metal/HCNS composite. (b) The large-area TEM image of HCNS-3; scale bar = 1 mm. (c) The cy-
cling test of the 3 wt % Pt/HCNS-3 (50 mg) sample under l > 420 nm irradiation. Reprinted with permission from ref. [46a]. Copyright T 2012 Macmillan Pub-
lishers Limited.

synthesis of hollow nanospheres sized melon or g-C3N4 poly- formance. For instance, Boron-doped carbon nitride was syn-
mer was reported using silica nanoparticles as templates (Fig- thesized for photocatalytic hydrogen production.[48a] Sodium
ure 7).[46a] These hollow nanospheres were beneficial for light- tetraphenylboron (Ph4BNa) was used as a doping source for
harvesting with highly improved photocatalytic activity for H2 the “bottom-up” polycondensation of urea, and boron atoms
generation, corresponding to an AQE of 7.5 %. Likewise, Zheng can modify g-C3N4 nanosheets in situ to tune the surface
et al. developed a facile method to fabricate hollow g-C3N4 chemistry by imparting acid sites on the surface of g-C3N4 ma-
spheres (HCNS) modified by Pt and Co3O4 nanoparticles (NPs) terials. Br-doped g-C3N4 semiconductors was synthesized via
onto the interior and exterior surface, respectively, to further a facile method for photoredox water splitting.[48c] The modifi-
promote the surface redox functions for enhancing photocata- cation of Br into g-C3N4 modulated the texture, optical absorp-
lytic water splitting activity.[46b] The enhanced activity was at- tion, conductivity, charge-carrier transfer rate, as well as photo-
tributed to the orientation transfer of photoexcited electron/ catalytic performance, without destroying the major construc-
hole pairs and spatially separated reactive sites for the evolu- tion and architecture of the g-C3N4 polymer. Nitrogen self-
tion of H2 and O2, thereby decreasing the unwanted charge re- doped g-C3N4 (N-g-C3N4) was synthesized by using melamine
combination and prohibiting the side reaction of water synthe- pre-treated with hydrazine hydrate to provide more nitro-
sis. Another g-C3N4 photocatalyst with highly open-framework gen.[48e] The average hydrogen evolution rate for N-g-C3N4 was
assembled from 2D nanosheets was fabricated using KCC- 1.8 times higher than that of pristine g-C3N4, due to the greatly
1 silica as the template.[46c,d] With unique nanostructure of the improved optical, emission and electronic properties. Novel
nanosheets beneficial for charge separation, highly improved porous P-doped g-C3N4 nanosheets showed a high visible-light
H2 evolution was observed on 3 wt % Pt/g-C3N4 with an AQE of photocatalytic H2-production rate of 1596 mmol h@1 g@1 and an
9.6 % at 420 nm. In addition, g-C3N4 microsphere photocata- AQE of 3.56 % at 420 nm, representing one of the most highly
lysts can also be prepared via a template-free solvothermal ap- active metal-free g-C3N4 photocatalysts.[48g] Sulfur-doped g-
proach with post-heating treatment.[46e] C3N4 was presented with a unique electronic structure, which
Although a large array of structures have been explored, the showed a H2 production rate 7.2 and 8.0 times higher than
uniformity and stability of existing materials are still far from those of C3N4 under l > 300 and 420 nm illumination, respec-
satisfying the sustainable applicaiton. Various factors such as tively (Figure 8).[48h] With abundant orbital electrons, metal ele-
low crystallinity, surface defects and structural collapse affect ments can aslo affect the optical and electric properties of g-
the charge transfer and separation, surface kinetics of redox re- C3N4. The impregnation of cobalt ions in g-C3N4 framework
actions and durability in the whole system. Accordingly, great was investigated to liberate O2 from water at soft materials in-
effort is still required to control the uniform and surface prop- terface.[48i] Iron doped g-C3N4 was prepared via a mild one-pot
erties of g-C3N4. In addtion, post thermal-treatment may lead method.[48j] The as-prepared photocatalyst presented a high
to enhanced crystallinity, stability and total efficiency. visible light-driven hydrogen evolution of ~ 16.2 mmol g@1 h@1
and an AQE of 0.8 %.
Although doping provides useful ideas for designing effi-
2.3. Doping
cient g-C3N4 photocatalysts, some issues still exist. For exam-
Doping is considered as a promising strategy to tune the band ple, lower oxidizing and reducing ability along with narrowing
structure, enhance the light adsorption and improve the per- the band gap, the presence of surface trapping center, or diffi-
formance of photocatalysts.[47] Some non-metal elements such cult to determine the doping site etc. Thus, further developing
as boron,[48a] fluorine,[48b] bromine,[48c] iodine,[48d] nitrogen,[48e] new doping methods and keeping a good balance of lower
oxygen,[44b, 48f] phosphor[37, 48g] and sulfur[48h] have been devel- redox capability to achieve a higher photocatalytic activity are
oped as efficient dopants to modify g-C3N4 with high per- highly desirable.

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1430 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Figure 8. (a) Schematic illustration of band structure evolution of S doped g-C3N4. (b) Atomic structure model of melem units substituted by sulfur atom
marked with blue spheres. (c) The cycling of H2 evolution by Pt-deposited C3N4 (a) and C3N4@xSx (b) under l > 300 and 420 nm, respectively. Reprinted with
permission from ref. [48h]. Copyright T 2010, American Chemical Society.

2.4. Defect engineering enhance photocatalytic performance by remedying the amino


groups and triazine structure inside g-C3N4 was also report-
In addition to interfacial engineering, nanostructural control, ed.[53] In addition, melamine remediation induced the forma-
and doping, introducing defects in g-C3N4, namely defect engi- tion of g-C3N4/mpg-C3N4 junctions, which also favored charge
neering, is also efficient to improve its photocatalytic activity. separation and electron transfer during the photocatalytic re-
Such strategies including the introduction of carbon vacan- action. The obtained g-C3N4 exhibited a H2 evolution rate that
cies,[49] nitrogen vacancies,[50] dye,[51] cyanamide defects,[52] re- was 6.5 times of that of the pristine g-C3N4.
ducing defects,[53] protonation,[54] alkalinized treatment,[55] An amorphous g-C3N4 (ACN) with a band gap of 1.90 eV was
vacuum heat-treatment,[56] oxygenation,[57] amorphization[58] obtained by simply heating partially crystalline g-C3N4 (GCN)
and breaking of hydrogen bonds[59] have also been investigat- with a band gap of 2.82 eV (Figure 9).[58] Due to synergistic
ed in recent years. effect of a wider photoabsorption range and suppressed
Creating vacancies in g-C3N4 is also efficient for enhanced charge carrier recombination, the obtained photocatalyst ex-
photocatalytic water splitting. For example, carbon vacancies hibited a much superior activity in H2 evolution than that of
were successfully introduced into holey g-C3N4 (HGCN) nano- the GCN. Kang et al. also reported a g-C3N4 with significantly
sheets via a thermally treating method, which exhibited a pho- enhanced photocatalytic H2 evolution activity under visible
tocatalytic H2 evolution rate 20 times higher than that of bulk light, modified by optimally breaking hydrogen bonds in the
g-C3N4 (BGCN).[49] Nitrogen-defective g-C3Nx was fabricated via layered g-C3N4.[59] As a result of volume shrinkage with the
a novel one step KOH-assisted approach during the thermally breaking of hydrogen bonds, abundant pores were formed
polymerizing precursors.[50b] The introduction of nitrogen de- throughout the whole particles. Due to the destruction of in-
fects could broaden the g-C3Nx absorption region which could tralayer long-range atomic order and loss of partial nitrogen
be easily tuned by the KOH/urea ratio. Due to enhanced visi- atoms, band tails or localized states close to the band edges
ble-light absorption and promoted charge-carrier separation, was increased. Both of the strategies mentioned above not
the obtained g-C3Nx exhibited superior photocatalytic H2 evolu- only promoted the charge separation/transfer, but also en-
tion performance compared to pristine g-C3N4 under visible hanced visible light absorption.
light illumination. The g-C3N4 polymer filled with cyanamide
defects yielded the H2 evolution rate and AQE (400 nm) of 12
3. Conclusions and Outlook
and 16 times higher than the unmodified melon, respective-
ly.[52a] Computational modelling and material characterization With excellent aqueous stability and suitable band gap, g-C3N4
demonstrated that these defects improved coordination to the is a promising visible-light-driven photocatalyst for water split-
Pt co-catalyst and enhanced the separation of the photoexcit- ting. Nevertheless, the photocatalytic activity of pure g-C3N4 is
ed electrons and holes. In parallel, introducing defects in g- low, due to severe charge recombination and poor surface ki-
C3N4 was an efficient method to enhance photocatalytic H2 netics. Thus, strategies for modifying g-C3N4 toward efficient
generation, which reduced the band gap from 2.7 to 2.0 eV.[52b] solar water splitting are of significant importance. This review
This defective g-C3N4 was synthesized by introducing H2 gas in provides a critical overview of the state-of-the-art strategies for
the thermally condensing precursors. With this defect engi- the modification of g-C3N4-based photocatalysts for water split-
neered g-C3N4, it showed 4.8 times higher than the pristine g- ting. In particular, we categorized a number of interfacial engi-
C3N4 for H2 generation under visible light irradiation. Further- neering approaches to design efficient g-C3N4 based hetero-
more, a facile melamine-based defect-remedying strategy to structures, including carbon/g-C3N4 junction, cocatalyst/g-C3N4

Chem. Asian J. 2017, 12, 1421 – 1434 www.chemasianj.org 1431 T 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Focus Review

Figure 9. (a–b) Schematic of crystalline GCN and ACN monolayer. (c) XPS valence band spectra. (d) Band alignments comparing GCN with ACN. (e) Photocata-
lytic H2 evolution with GCN and ACN under visible light (l > 440 nm). (f) Wavelength-dependent H2 evolution with ACN. Reprinted with permission from
ref. [58]. Copyright T 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

junction, polymer/g-C3N4 junction, semiconductor/g-C3N4 junc- tocatalysts, the structural property is one of the most critical
tion, and g-C3N4/g-C3N4 isotype junction. These heterostruc- factors that affect the whole photocatalytic performance, be-
tures have exhibited their features in accelerating charge sepa- cause it largely determines the efficiency of mass transfer and
ration and transportation, prolonging charge carrier lifetime the number of reaction sites. From the perspective of practical
and promoting surface reaction kinetics. Moreover, nanostruc- applications, it is anticipated that g-C3N4-based photocatalysts
tures such as 1D rod-like nanostructures, 2D sheet-like nano- will receive further research attention and may play a more im-
structures, 3D sphere-like nanostructures and some other spe- portant role in the field of solar-driven water splitting.
cial nanostructures also affect the photocatalytic water split-
ting performance of g-C3N4. Other strategies such as doping
and defect engineering are also effective to enhance the pho-
Acknowledgements
tocatalytic activity of g-C3N4.
This work is financially supported by National Science Founda-
Although significant progress has been achieved in g-C3N4-
tion of China (No. 51471006, No. 51534009, No. 51225402), Bei-
based photocatalysis, the research in this field is at its early
jing Natural Science Foundation (No. 2151001, 2154043), Scien-
stage from the perspective of practical applications. The main
tific research project of Beijing Municipal Education Commis-
challenges that must be overcome for g-C3N4-based photoca-
sion (No. KM201610005026) and Beijing High-level Talents pro-
talyst involve: 1) the fundamental mechanisms of photocatalyt-
gram (2017). The financial support from Australian Research
ic enhancement for the g-C3N4-based photocatalytic systems is
Council through its DP and FF programs is also highly appreci-
complicated or even unclear in some systems. Some in situ
ated. Y. Yang acknowledges the financial support from China
characterization to monitor the photocatalytic reaction and in-
Scholarship Council. S. Wang acknowledges the support from
terfacial engineering can be very powerful. 2) Narrowing the
Australian Government Research Training Program and UQ
band gap can induce a broader photo-absorption range, but
Centennial Scholarships.
reduced redox capability of g-C3N4 due to the sacrifice of po-
tential energy. It is still challenging to keep the balance of vari-
ous factors to achieve the optimal photocatalytic activity. Conflict of interest
3) Some explanations of photocatalytic activity on the g-C3N4-
based photocatalyst are still controversial or even inconsistent. The authors declare no conflict of interest.
Therefore, more studies are required for developing the intrin-
sic understanding of the enhancement of g-C3N4 based nano-
Keywords: doping · graphitic carbon nitride ·
composites, especially employing some advanced characteriza-
heterojunctions · nanostructures · water splitting
tion techniques. Also, it is important to develop standardized
conditions to measure the photocatalytic activity including ir-
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