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Recent progress on graphene-based photocatalysts: current status and future
perspectives
Nan Zhang, Yanhui Zhang and Yi-Jun Xu*
Received 13th June 2012, Accepted 25th July 2012
DOI: 10.1039/c2nr31480k
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

Graphene (GR) has become a sparkling rising star on the horizon of material science. Due to its unique
planar structure, excellent transparency, superior electron conductivity and mobility, high specific
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surface area, and high chemical stability, GR is regarded as an ideal high performance candidate to
prepare GR-based nanocomposites for energy storage and conversion. During the past few years, GR-
based photocatalysts have been attracting ever-increasing research attention. In this tutorial review, the
applications of GR-based nanocomposites in photocatalysis, including nonselective processes for
degradation of pollutants, selective transformations for organic synthesis and water splitting to clean
hydrogen energy, are summarized systematically. In particular, in addition to discussing opportunities
offered by GR, we will also describe the existing challenges for future exploitation and development of
GR-based nanocomposites, which we hope would significantly advance us to rationally and efficiently
harness the outstanding structural and electronic properties of GR to design smarter and more efficient
GR-based photocatalysts instead of joining the graphene ‘‘gold rush’’.

State Key Laboratory Breeding Base of Photocatalysis, College of
Chemistry and Chemical Engineering, Fuzhou University, Fuzhou
350002, Fujian, P.R. China. E-mail: yjxu@fzu.edu.cn; Fax: +86 591
83779326; Tel: +86 591 83779326
1. Introduction
Dating back to October 2004, a revolution in science and tech-
nology was triggered by the report that condensed-matter
physicists Geim and Novoselov had prepared two-dimensional
sheets of carbon atoms—graphene (GR).1,2 GR, as an allotrope
of carbon, is composed of layers of carbon atoms packed into a
honeycomb network that can be exfoliated from bulk graphite

Nan Zhang was born in Hebei, Yanhui Zhang was born in

P. R. China, in 1987. She
received her bachelor degree in
chemical engineering & tech-
nology from East China Insti-
tute of Technology (2009), P.
R. China. Currently, she is
pursuing her PhD degree with
the supervision of Prof. Xu at
the National Research Center
for Environmental Photo-
catalysis Engineering and Tech-
nology, Fujian Provincial Key
Nan Zhang Laboratory of Photocatalysis-
State Key Laboratory Breeding
Base, College of Chemistry and
Chemical Engineering, Fuzhou University, P. R. China. Her main
research interests include the fabrication of core–shell and carbon-
based nanocomposites for potential target applications in hetero-
geneous photocatalysis.
Fujian, P. R. China in 1986. He
received his bachelor degree in
applied chemistry from
Zhangzhou Normal University
(2009), P. R. China. Currently,
he is pursuing his PhD degree
with the supervision of Prof. Xu
at National Research Center for
Environmental Photocatalysis
Engineering and Technology,
Fujian Provincial Key Labora-
tory of Photocatalysis-State
Yanhui Zhang Key Laboratory Breeding Base,
College of Chemistry and
Chemical Engineering, Fuzhou
University, P.R. China. His main research interests include the
synthesis of nanostructured materials, especially graphene-based
composites nanomaterials for applications in heterogeneous
photocatalysis.

5792 | Nanoscale, 2012, 4, 5792–5813 This journal is ª The Royal Society of Chemistry 2012

using different approaches, including thermal exfoliation,
mechanical cleavage, chemical vapor deposition, and chemical
functionalization.3–10 Recent years have witnessed a cornucopia
of approaches toward the exploration of GR, this sparkling
rising star on the horizon of material science.11–13 Considering its
planar state, GR can be wrapped up into zero-dimensional
spherical fullerenes with the introduction of pentagons, rolled
along a given direction into one-dimensional carbon nanotubes
or staked into three-dimensional graphite.1 Hence, GR is
recognized as the basic building block of all-dimensional carbon
materials. Its lamellar structure bestows remarkable and unique
properties, such as a high mobility of charge carriers (>200 000
cm2 V
1 s
1 at electron densities of 2  1011 cm
2), exceptional
Young’s modulus values (1.0 TPa), large spring constants (1–
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
5 Nm
1), theoretically high specific surface area (2630 m2 g
1),
excellent thermal conductivity (5000 Wm
1 K
1) and optical
transmittance (97.7%),14 which have spurred enormous interest
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in the scientific and industrial communities. On account of its
favorable characteristics, GR has been utilized in diverse areas,
such as nanoelectronics, optoelectronics, chemical and
biochemical sensing, polymer composites, H2 production and
storage, intercalation materials, drug delivery, supercapacitors,
catalysis and photovoltaics.15–62
Among various topics, the fabrication of GR-based catalysts,
especially those for photocatalysis, is currently an important
issue of particular concern. In the 21st century, aggravating
energy and environmental problems such as pollution, fossil fuel
depletion and global warming are ringing the alarm bells for
human society.46 Photocatalysis has attracted intense attention
during the past decades because of its potential for environ-
mental purification and converting photon energy into chemical
energy.12,16 This green technology has been widely applied to
nonselective processes for the degradation of pollutants, selective
organic transformations for synthesis of fine chemicals, water
splitting to hydrogen energy and other photoelectrochemical
processes in both the gas and liquid phases.63–86 However, the
practical applications of this technique are limited by the
Prof. Yi-Jun Xu received his
PhD degree in heterogeneous
catalysis at the School of
Chemistry, Cardiff University,
U.K. in 2006 with Prof. Graham
J. Hutchings (FLSW FRS).
From 2007 to 2009, he worked
as a postdoctoral fellow at the
Fritz Haber Institute of the Max
Planck Society, Berlin, Ger-
many. After that, he joined the
faculty as a Minjiang Scholar
Professor at Fuzhou University.
Yi-Jun Xu His current research interests
are mainly focused on synthe-
sizing nanostructured materials,
such as graphene-based nanocomposites and core–shell nano-
structured materials, and exploring their applications in the area of
heterogeneous photocatalysis.
This journal is ª The Royal Society of Chemistry 2012
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inability to utilize visible light, insufficient quantum efficiency, or
the possible photodegradation of the catalyst. Designing novel
catalysts to meet these technical needs is still a challenge. Due to
its unique atom-thick 2D structure, excellent transparency, high
specific surface area, locally conjugated aromatic system, supe-
rior electron mobility, and high chemical, electrochemical
stability, GR is regarded as an ideal high performance candidate
for photocatalyst carriers or promoter.46 That is, to synthesize
GR-based nanocomposites toward specific photocatalytic reac-
tion opens up a new promising pathway for the further devel-
opment of photocatalysis.
It is undoubted that the discovery of GR brings about enor-
mous opportunities for science and technology. Although there
have been vast numbers of reports on GR, including exploration
of novel approaches to synthesize GR or GR-based nano-
materials and their utilization,10,87–96 most of them typically
involve introduction of GR merely for the sake of GR itself via
relatively simplistic methods such as mixing instead of putting it
into full play with elaborate design. The improvements seen with
the optimization of preparation methods and making full use of
GR are still unsatisfactory.45 Therefore, research attention
should focus on how to utilize fully GR, rather than separately
imposing hype on the ‘miracle of GR’ in much the same way as
its carbon forebears (fullerenes or carbon nanotubes), which
could significantly advance our rational fabrication of smart
GR-based nanocomposites for various applications.78
This tutorial review aims to give a relatively systematic,
updated summary of the current status of GR-based nano-
composites applied in photocatalysis, including nonselective
degradation of pollutants, selective transformations for organic
synthesis of fine chemicals and water splitting to clean hydrogen
energy. Notably, the application of GR-based nanocomposites
in photocatalytic selective transformation is not covered by
previous reviews.12,16,45,46,48 Furthermore, some challenges con-
fronted by GR-based photocatalysts are discussed in the future
perspectives section. It is hoped that this updated review would
promote us to harness efficiently and rationally the outstanding
structural and electronic properties of GR to design more effi-
cient GR-based photocatalysts toward numerous applications in
conversion of solar to chemical energy. As the editorials pub-
lished in Nature put it,97 GR is not a miracle material, just a very
promising one and it will take restraint and sustained interest to
deliver its potential. Although the hunt is on for applications that
can exploit graphene’s remarkable properties, the research work
necessary to find out how it could best be harnessed remains
relatively incomplete. Such targeting of graphene’s potential will
be vital to its success including its application in photocatalysis.
What we should do is to exploit its properties and applications in
a more reasonable and rational way instead of joining the gra-
phene ‘‘gold rush’’.97
2. Photocatalytic nonselective processes
Nonselective photocatalysis has been attracting research interest
because of its great potential for environmental remediation,
such as the removal of stubborn, noxious compounds or non-
biodegradable molecules from air, soil and water.15,98–103 During
these nonselective processes, the contaminants are mineralized
into stable inorganic compounds such as carbon dioxide, water
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and salts. On account of the superior electron conductivity and
mobility, high adsorption capacity, high specific surface area and
transparency of graphene (GR), GR-based nanocomposites can
serve as a new type of promising photocatalyst and have been
utilized in the nonselective degradation of pollutants for envi-
ronmental amelioration.104–177 Kamat’s group178 has demon-
strated the capability of reduced graphene oxide (RGO) to store
and shuttle electrons via a stepwise electron transfer process and
to serve as a catalyst nanomat (Fig. 1), which confirms the
feasibility of applying GR in photocatalysis and paves the way
for the development of next generation catalyst systems.
Li and coworkers109 have prepared a chemically bonded TiO2
(P25)–graphene (GR) nanocomposite via a facile one-step
hydrothermal method using graphene oxide and P25 as the
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
precursors. It can be seen from Fig. 2A that the introduction of
GR causes the bandgap narrowing of P25, which should be
attributed to the chemical bonding between P25 and GR.109 The
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results of photoactivities demonstrate that P25–GR exhibits
enhanced activity toward the photodegradation of methylene blue
(MB) compared to the bare P25 under both UV and visible light
irradiation. Moreover, it also shows higher photodegradation
rate than the P25–CNTs with the same carbon content, as dis-
played in Fig. 2C and D, which can mainly be ascribed to the giant
2D planar structure, and enhancement of the adsorption of dyes
and of charge carrier transportation due to the addition of GR.
The tentative processes of photodegradation of MB over P25–GR
are illustrated in Fig. 2B. This work opens new possibilities in the
application of TiO2–carbon composites as photocatalysts for
environmental protection. However, the effect of different weight
addition ratios of carbon materials on the photocatalytic
Fig. 1 (A) Schematic illustration of selective catalysis at different sites
on RGO as a 2-D conducting support, and (B) photographs showing the
color changes observed during stepwise transfer of electrons: ① storing
electrons in TiO2 by irradiating the deaerated ethanol suspension with
UV light (l > 300 nm) for 30 min; ② addition of deaerated ethanol
suspension of GO until no blue color remains (gray-colored solution
results due to the formation of RGO); ③ reduction of Ag+ to Ag
nanoparticles (red color) by stored electrons in RGO following the
addition of deaerated AgNO3 solution. Reprinted with permission from
ref. 178. Copyright 2010, American Chemical Society.
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Fig. 2 (A) Diffuse reflectance absorption spectra of P25–GR; (B)
schematic structure of P25–GR and tentative processes of the photo-
degradation of MB over P25–GR; comparison of photocatalytic activity
in the degradation of MB under (C) UV light (l ¼ 365 nm) and (D) visible
light (l > 400 nm) over (1) P25, (2) P25–CNTs, and (3) P25–GR pho-
tocatalysts. Reprinted with permission from ref. 109. Copyright 2010,
American Chemical Society.
performance is not taken into account. Consequently, it may be
insufficient to conclude that the TiO2–graphene composite is
essentially different from other TiO2–C (fullerene, carbon nano-
tube, or activated carbon) composites in enhancement of the
photocatalytic activity of TiO2.15
With the unaddressed fundamental issue, our group15
prepared a series of TiO2–carbon nanocomposites with different
weight addition ratios of carbon materials to investigate the
difference of graphene (GR) compared with other carbon
materials, e.g., carbon nanotubes (CNTs), on improving the
photoactivity of semiconductor TiO2. We found that the intro-
duction of GR into the matrix of TiO2 could enhance the stability
and activity of TiO2 in the photodegradation of pollutants, as
shown in Fig. 3. However, the higher addition of GR leads to the
deterioration of photoactivity. All of these features can also be
observed in TiO2–CNT composites. Our results indicate that
TiO2–GR composite should be in essence the same as other
TiO2–carbon materials in the enhancement of the photocatalytic
activity of TiO2. More attention should be paid to rationally
design TiO2–GR composites in a more reasonable way.
In addition to coupling GR with semiconductor nanoparticles,
there are some other reports using the semiconductor precursor
with specific morphology, such as nanorods and nanotubes. For
instance, self-assembly of TiO2 nanorods on the graphene oxide
sheets (GO–TiO2 NRCs) has been achieved by a water/toluene
two-phase process.139,140 Compared with GO–P25 and the original
TiO2 nanorods, the GO–TiO2 NRCs exhibit higher photocatalytic
activity toward degradation of contaminant methylene blue (MB)
and acid orange 7 (AO 7) under UV light irradiation.139,140
Obviously, the above research works all focus on simply
random ‘‘hard’’ integration of pre-synthesized or commercially
available semiconductor solids with GO sheets as also reported
in some other works.117–119,126,128,131,134,138 Such an ex situ
hybridization makes pre-selection of nanostructures with desired
functionalities possible; however, it cannot make good use of the
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Fig. 3 Photocatalytic performance the P25–GR nanocomposites for gas-phase photocatalytic degradation of (a) benzene, (b) mineralization ratio and
liquid-phase photocatalytic degradation of MB under the irradiation of (c) UV light (l ¼ 365 nm), (d) visible light (l > 400 nm); (e) the proposed
schematic illustration showing the reaction mechanism for photocatalytic degradation of organic pollutants over the P25–GR in which pink spheres and
black sheet represent TiO2 nanoparticles and GR, respectively. Reprinted with permission from ref. 15. Copyright 2010, American Chemical Society.

structural advantages of GR, thus suffering from a low-density
and non-uniform coverage of the particles on GR sheets and
poor interfacial contact between the semiconductors and GR,
which is unfavorable for GR to play its role during the photo-
catalytic processes.47,78 In contrast, an in situ crystallization
which allows the precursors of GR and metal compound to pre-
mix together can mitigate these problems and result in a uniform
coverage of nanocrystalline semiconductor nanoparticles on GR
sheets, thus favoring improvement of the photocatalytic
performance.
For example, Du et al.148 have fabricated hierarchically
ordered macro-mesoporous TiO2–graphene composite films
through a confinement self-assembly method. As illustrated in
Fig. 4A, macro-mesoporous TiO2–graphene composite films are
prepared by adding graphene oxide (GO) to the system of
colloidal crystals assembled from monodisperse polystyrene (PS)
spheres with controlled sizes and subsequently reducing GO in
situ within the films. The obtained samples are designated as
(GR)–Ti–(Ma170/200)–Me, for which the presence of bracketed
components depends on the preparation process. The diameter

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Fig. 4 (A) Illustration for the preparation of a macro–mesoporous
TiO2–graphene composite film; (B) typical SEM and (C) TEM micro-
graphs of a macro–mesoporous TiO2–graphene composite film assem-
bled from 300-nm diameter polystyrene spheres; (D) photocatalytic
degradation of MB under UV light irradiation (l ¼ 365 nm) using (a) Ti–
Me, (b) GR–Ti–Me, (c) Ti–Ma200–Me, (d) GR–Ti–Ma200–Me, (e) Ti–
Ma170–Me, and (f) GR–Ti–Ma170–Me films. Reprinted with permission
from ref. 148. Copyright 2011, American Chemical Society.
of Ma170/200 replicated by the PS template spheres is ca. 240/300
nm, respectively. It can be seen from Fig. 4B and C that 3D
ordered macropores are formed. Due to the specific, hierarchical
structure and the introduction of GR, these TiO2–GR films show
Fig. 5 (A and B) representative TEM images of TGC3 with 12 hours solvothermal time (the inset of B shows the SAED pattern); variation of
normalized C/C0 for phenol with time under (C) visible light irradiation (l > 410 nm) and (D) UV light irradiation (l ¼ 365 nm; C0: the initial phenol
concentration after adsorption equilibrium). Reprinted with permission from ref. 150. Copyright 2011, John Wiley & Sons, Inc.
5796 | Nanoscale, 2012, 4, 5792–5813
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an enhanced capacity to rapidly adsorb and photodegrade
organic dyes under UV light irradiation (Fig. 4D). These mate-
rials, with a hierarchical structure and morphology composition,
could potentially provide an attractive opportunity for envi-
ronmental purification.
In another report, TiO2–graphene composites (TGC) have
been synthesized by a facile wet chemistry route during which the
TiO2 nanoparticles in situ grow in the interlayers of expanded
graphite (EG) accompanied by the simultaneous exfoliation of
EG under ethanol-assisted solvothermal conditions.150 It can be
observed from Fig. 5A and B that the TiO2 coating is uniform on
the graphene surface. These thermally treated composites
obtained under different experimental conditions possess a
higher photocatalytic efficiency for the degradation of phenol
than P25 under both visible and UV lights (Fig. 5C and D).
It is known that crystals usually exhibit the specific surface-
dependent properties. As for anatase TiO2, the {001} facets are
the most reactive facets with a high surface energy.179 There are
some studies on the nanocomposites consisted of anatase TiO2
with exposed {001} high-energy facets and graphene.151,152,174 For
instance, nano-sized anatase TiO2 sheets mainly dominated by
{001} facets have been prepared on graphene sheets (T–GS) via a
facile solvothermal route, as shown in Fig. 6A–D.152 In
comparison with commercial P25 and pure TiO2 nanosheets, the
composite exhibits significant improvement in photocatalytic
degradation of the azo dye Rhodamine B (RhB) under visible
light irradiation (Fig. 6E and F), which results from the effective
charge anti-recombination of graphene and the high catalytic
activity of {001} facets. Such a unique structure and advanced
chemical constitution holds promise for environment remedia-
tion and energy conversion such as solar cell and water splitting.
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Fig. 6 (A) Schematic flowchart of the formation of TiO2–graphene
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nanosheets (T–GS); (B) schematic of tetrabutyl titanate grafted on the
GO surface by chemisorption; (C and D) typical TEM images of
T–GS–6 h; (E) liquid-phase photocatalytic degradation of RhB under the
irradiation of visible light (l > 400 nm) and (F) photocatalytic degra-
dation reaction kinetics of RhB over P25, T–GS–6h and pure TiO2
nanosheets. Reprinted with permission from ref. 152. Copyright 2012,
Royal Society of Chemistry.
Beyond the most studied photocatalyst TiO2, some attention
has been devoted to other semiconductors coupled with gra-
phene.108,113,117,119,126–128,135,145,153,156,157,173 For example, Zou
et al.157 have prepared sandwich-like metal oxide/graphene/metal
oxide (MO/G/MO) heterostructures by a simple and general
nanocrystal-seed-directed (NSD) hydrothermal route, which
realizes large-scale growth of nanorod arrays of various semi-
conductor metal oxides, including TiO2, ZnO, MnO2, CuO, and
ZrO2 on both sides of flexible graphene sheets (Fig. 7a–f). They
found that in the NSD hydrothermal processes, the MO nano-
crystals seeded on the graphene sheet play a key role in growth of
the nanorod arrays on the graphene surfaces; the size of the
nanocrystal seeds on the graphene sheets has an obvious effect on
the size of the nanorods grown on the graphene sheets. The
photocatalytic property of the TiO2/G/TiO2 has been evaluated
by degradation of methylene blue (MB) under UV/Vis
Fig. 7 (a) Schematic of the growth process of metal oxides nanorods on
both sides of graphene sheets by the NSD hydrothermal route; (b–f) SEM
images of sandwich MO/G/MO heterostructures obtained by the NSD
hydrothermal route: (b) TiO2/G/TiO2, (c) ZnO/G/ZnO, (d) MnO2/G/
MnO2, (e) CuO/G/CuO, (f) ZrO2/G/ZrO2; (g) photocatalytic degradation
of MB under UV/Vis irradiation with a 500 W Xe lamp. Reprinted with
permission from ref. 157. Copyright 2011, John Wiley & Sons, Inc.
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irradiation. As displayed in Fig. 7g, compared with P25 and TiO2
nanorods, TiO2/G/TiO2 catalysts exhibit remarkably enhanced
photocatalytic performance, indicating that MO/G/MO hetero-
structures can serve as promising candidates for photocatalytic
decontamination. Besides, these heterostructures with highly
ordered nanoscale texturing on flexible substrates could provide
potential opportunities for flexible-device fabrication with
optimal performance, such as field-effect transistors, field emis-
sion displays, photocatalysis, and energy-harvesting devices.
Besides the conventional semiconductors, it is desirable to
develop unique yet efficient hybridizers for the visible-light
drivable and recyclable GO-based photocatalysts to provide
more varied and new opportunities for environmental remedia-
tion.114 An efficient visible-light-driven plasmonic photocatalyst
in terms of Ag/AgX/GO (X ¼ Br, Cl) nanocomposites fabricated
via a water/oil system at room temperature has been reported by
Zhu et al. (Fig. 8A and B).114 As shown in Fig. 8C and D, these
hybrids exhibit distinctly enhanced photoactivity for degradation
of methyl orange (MO) pollutant under visible light irradiation
due to the good adsorptive capacity of Ag/AgX/GO, the smaller
size of the Ag/AgX nanoparticles, the facilitated charge transfer,
and the suppressed recombination of electron–hole pairs in Ag/
AgX/GO. Subsequently, they found that Ag/AgBr/GO synthe-
sized through an oil/water microemulsion displays a higher
photocatalytic activity than that of the corresponding Ag/AgBr/
GO nanomaterial obtained by a water/oil microemulsion for
degradation of MO under sunlight irradiation, which can be
ascribed to the higher surface content of Ag and the higher mole
ratio of metallic Ag0 to Ag+ (Fig. 8E and F).115 Their investi-
gations open up new possibilities for development of stable and
efficient GO-based plasmonic photocatalysts to utilize visible
light as an energy source.
In addition to the aforementioned examples, increasing
interest has also been devoted to fabricating graphene-based
nanocomposite photocatalysts by developing new synthetic
strategies, such as premodification of graphene sheets and
Fig. 8 Typical SEM images of the synthesized (A) Ag/AgBr/GO, (B) Ag/
AgCl/GO nanospecies via a water/oil system and (C and D) the photo-
catalytic activities for photodegradation of MO under visible light irra-
diation (l > 400 nm); (E) schematic explanation for the one-pot
surfactant-assisted synthesis of Ag/AgBr-based nanostructures via an oil/
water (top panel) and a water/oil (bottom panel) microemulsion system;
(F) photocatalytic activities of Ag/AgBr-based plasmonic photocatalysts
for the photodegradation of MO under sunlight irradiation. Reprinted
with permission from ref. 114 and 115. Copyright 2011, 2012, American
Chemical Society.
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adopting aided techniques including electrostatic interaction,
electrospinning, electrodeposition, chemical vapor deposition
(CVD) and ultrasonication.107,113,124,127,129,154,155,159,161 For
instance, graphene oxide (GO)-wrapped amorphous TiO2
nanoparticles (NPs) have been synthesized by co-assembly of
positively charged TiO2 NPs with negatively charged GO
nanosheets, as illustrated in Fig. 9A.124 The SEM images indicate
that bare amorphous TiO2 NPs are entirely wrapped by GO
nanosheets; after a hydrothermal treatment for the reduction of
GO to GR and the crystallization of amorphous TiO2 NPs, the
dense precursors turn into porous nanospheres having a hierar-
chical structure that consists of interconnected nanocrystals with
intact graphene nanosheets (Fig. 9B–D). These GR–TiO2 NPs
exhibit enhanced photoactivity under visible light irradiation for
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
is schematically illustrated in Fig. 10j. Under visible light irra-
diation, the electron would transfer from the excited dye, RhB*,
to graphene. Since the work-functions of CNTs and Ni are much
higher than graphene, the injected electron on graphene plane
can continuously transfer to the CNTs and Ni particles, spatially
separating the RhB_+ radical and the electron, thus effectively
decreasing electron accumulation. Such CNT–RGO composites
represent a new family of innovative carbon materials for visible-
light-activated photocatalysis. Besides, they have prepared gold
or copper modified-graphene composite photocatalysts for dye
degradation under visible light irradiation.129,161 As shown in
Fig. 11, the graphene-based composites can possess enhanced
visible light photoactivities for dye degradation and the corre-
sponding photocatalytic mechanism is also proposed.129,161

degradation of methylene blue (MB), as shown in Fig. 9E. This In order to remove catalysts effectively and readily, magnetic
can be attributed to the bandgap narrowing of the hybrid components have also been introduced in the preparation of
material, which consequently allows enhanced absorption of magnetically separable graphene-based photocatalysts. The
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visible light and more efficient transfer of photogenerated elec-
trons from excited MB to TiO2 NPs through graphene nano-
sheets (Fig. 9F). This new synthetic strategy could enable a tight
integration of functional semiconductor NPs and graphene
nanosheets for the synthesis of highly photoactive graphene-
based metal oxide hybrid materials.
Zhao and coworkers121,129,159,161 have carried out a series of
studies on utilization of graphene in photocatalytic nonselective
processes. They pillared layered graphene oxide (GO) and
reduced graphene oxide (RGO) platelets with carbon nanotubes
(CNTs) using the CVD method with acetonitrile as the carbon
source and nickel nanoparticles as the catalysts (Fig. 10a–g).159
The composite materials with RGO layers pillared by CNTs
form a robust three-dimensional porous structure of specific
surface as high as 352 m2 g
1. The unique porous structure and
the excellent electron transfer properties of graphene provide the
CNT-pillared RGO composites with an excellent visible light
photoactivity in the degradation of Rhodamine B (RhB), as
shown in Fig. 10h and i. The proposed photocatalytic mechanism
composites of ZnFe2O4–graphene (G), MnFe2O4–G and
NiFe2O4–G have been prepared by Wang’s group.111,112,158
Under visible light irradiation, these graphene-based composite
photocatalysts are not only photoactive in degradation of
methylene blue (MB), but can also be separated easily, as dis-
played in Fig. 12.
Besides the applications of graphene-based nanocomposites in
the photodegradation of organic dyes in the liquid phase, they
have also been applied in the gas phase.15,133,169 Our group15 has
utilized TiO2–graphene nanocomposites for the photocatalytic
degradation of a volatile organic pollutant (VOC), benzene, in
the gas phase for the first time (Fig. 3a and b). We found that the
P25–GR nanocomposites exhibit much higher activity and
stability than the reference catalyst of bare P25. Afterwards,
nonstoichiometric TiO2–graphene nanocomposites have been
fabricated by thermal hydrolysis of a suspension of graphene
nanosheets and a titania–peroxo complex.133 The photoactivity is
assessed by the photodegradation of butane in the gas phase
under UV and visible light irradiation. It can be seen clearly from

Fig. 9 (A) Schematic illustration of synthesis steps for graphene-wrapped anatase TiO2 NPs and corresponding SEM images of (B) bare amorphous
TiO2 NPs, (C) GO-wrapped amorphous TiO2 NPs, and (D) graphene-wrapped anatase TiO2 NPs (scale bar: 200 nm); (E) photodegradation of MB
under visible light irradiation (l > 420 nm) by (a) P25, (b) bare anatase TiO2 NPs, (c) graphene–TiO2 NPs (two-step hydrothermal), and (d) graphene–
TiO2 NPs; (F) the suggested mechanism for the photocatalytic degradation of MB by graphene-wrapped anatase TiO2 NPs under visible light irra-
diation. Reprinted with permission from ref. 124. Copyright 2012, John Wiley & Sons, Inc.

5798 | Nanoscale, 2012, 4, 5792–5813 This journal is ª The Royal Society of Chemistry 2012
 View Article Online
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

Fig. 10 FESEM images of (a) GOCNT-30-17, (b) GOCNT-15-17, (c) GOCNT-30-9, (d) GOCNT-15-9, (e) RGOCNT-15-4, and (f) RGOCNT-15-0.6
(the samples were denoted as GO/RGOCNT-X-Y where X and Y refer to CVD time and the mass ratio of Ni/C); (g) experimental steps of pillaring GO
and RGO platelets with CNTs; (h) photocatalytic degradation for RhB under different experimental conditions with catalysts GOCNT-15-4 and P25; (i)
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photocatalytic properties of different samples in degrading RhB (l > 420 nm); (j) energy diagram showing the proposed mechanism of photosensitized
degradation of RhB under visible light irradiation. Reprinted with permission from ref. 159. Copyright 2010, American Chemical Society.

Table 1 that the sample labelled as TiPC0100 possesses the
highest photoactivity for gas-phase decomposition of butane
under UV and visible light irradiation. An increasing content of
graphene will lower the photodegradation rate, which has also
been observed for the gas-phase degradation of benzene over
P25–GR nanocomposites reported by our group.15
In addition, graphene-based nanocomposites have also been
utilized in the photoinactivation of bacteria.140,170,171 The TiO2–
graphene films (Fig. 13A) prepared via deposition of graphene
oxide platelets on TiO2 thin films followed by annealing and
irradiation process have been used for photocatalytic degrada-
tion of E. coli bacteria in an aqueous solution under solar light
irradiation.170 As shown in Fig. 13B, the sample irradiated for 4 h
exhibits the highest antibacterial activity and its activity is
improved by a factor of about 6 and 7.5 relative to the activity of
the annealed graphene oxide/TiO2 and the bare TiO2 thin film,
respectively. More recently, Akhavan’s group fabricated gra-
phene–tungsten oxide (GR–WO3) composite thin films with
sheet-like surface morphology.171 The GR–WO3 composite thin
films show an excellent visible light photocatalytic performance
in the photoinactivation of viruses as compared to WO3, which is
assigned to the formation of W–C and W–O–C bonds. Their
results could provide useful information for controlling the
effects of upcoming graphene-containing photocatalysts, which

Fig. 11 (A) TEM image of the reduced graphene oxide (RGO)–Au (the insets are an HRTEM image and particle size distribution of the Au particles);
(B) degradation of RhB over (a) RGO–Au in the dark, (b) without catalyst, (c) RGO, (d) P25, (e) P25–Au and (f) RGO–Au under visible light irradiation
(l > 420 nm); (C) the proposed mechanism of photosensitized degradation of dyes over RGO–Au under visible light irradiation; (D) degradation of RhB
over RGOCu–NO3 in the dark (,), without catalyst (<), RGO (C), P25 (:), RGOCu–Cl (B), and RGOCu–NO3 (A) under visible light irradiation
(l > 420 nm) (the insets are TEM and HRTEM images of RGOCu–NO3); (E) the possible mechanism of photosensitized degradation of dyes over
RGOCu composite under visible light irradiation. Reprinted with permission from ref. 129. Copyright 2011, John Wiley & Sons, Inc. Reprinted with
permission from ref. 161. Copyright 2010, Royal Society of Chemistry.

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Fig. 13 (A) AFM image of graphene oxide/TiO2 thin films exposed to

UV visible light irradiation for 4 h in the photocatalytic reduction
process; (B) number of bacteria cultured from the viable E. coli on the
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

surface of the graphene oxide/TiO2 thin films reduced by UV visible light-

assisted photocatalytic process for (a) 0, (b) 0.5, (c) 1, (d) 2, and (e) 4 h
Fig. 12 Typical TEM images of (a) ZnFe2O4–G, (c) MnFe2O4–G (the irradiation time, (f) bare TiO2 thin film, (g) graphene oxide/glass film
inset is the particle size distribution for MnFe2O4), (e) NiFe2O4–G and under solar light irradiation and (h) graphene oxide applied as in part g
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(b, d and f) the corresponding photocatalytic activities for degradation of
MB under visible light irradiation with different catalysts (l > 420 nm)
(the inset is the magnetic separation property of the nanocomposite).
Reprinted with permission from ref. 111 and 158 (Copyright 2012, 2011,
American Chemical Society) and from ref. 112 (Copyright 2012, John
Wiley & Sons, Inc).
work efficiently on the destruction of environmental bio-organ-
isms under solar light irradiation.171
but in the dark, as a control sample. Reprinted with permission from ref.
170. Copyright 2009, American Chemical Society.
leading to better separation of the photogenerated carriers
(Fig. 14f) over GR–TiO2 as compared to CNT–TiO2. From
Table 2, it can be seen that TiO2–5% GR can photocatalyze a
range of benzylic alcohols and allylic alcohols to the corre-
sponding aldehydes under visible light irradiation with high

3. Photocatalytic selective organic transformations

Growing endeavors have been devoted to applying photo-
catalysis, a green technique, to photocatalytic selective trans-
formations.71,73,76,86,180,181 Although photocatalytic processes
have often been thought to be highly unselective, recent progress
indicates that semiconductor photocatalysis can also serve as an
alternative to conventional synthetic routes for synthesis of fine
chemicals through the selection of appropriate semiconductors
and control of the reaction conditions.78,79,84,86,169,182–187 It is now
recognized that heterogeneous photocatalysis holds great
potential for organic synthesis due to its possibility to avoid
environmentally detrimental heavy metal catalysts, strong
chemical oxidants or reducing agents, such as CrIV, MnO4
,
ClO
, Cl2, H2 and CO, as well as harsh reaction conditions such
as high temperature and high pressure.80,83,188,189 Hitherto, as
mentioned above, most reports on graphene-based nano-
composites often focus on their applications in nonselective
processes for environmental protection, whereas the utilization
for selective organic transformations is relatively scarce.
Our group has carried out a series of relative studies in this
respect.78,79,182,183 We have prepared graphene–TiO2 nano-
composites by interfacial engineering of the unique 2D mat of
GR with TiF4 as precursor via a facile two-step wet-chemistry
approach and applied them for selective oxidation of alcohols to
aldehydes using dioxygen as oxidant under mild conditions.78
Fig. 14 (a) Time-online profile of yield of benzyl aldehyde from selective
Compared with its analogue CNT–TiO2 featuring a poor inter-
oxidation of benzyl alcohol over TiO2–5% GR and TiO2–5% CNT
facial contact, the GR–TiO2 nanocomposites featuring an inti- nanocomposites under visible light irradiation (l > 400 nm); (b) SEM, (c)
mate interfacial contact exhibit enhanced visible light TEM and (d) HRTEM images of TiO2–5% GR; (e) TEM image of TiO2–
photoactivity, as displayed in Fig. 14a. The superior structure- 5% CNT; (f) photocurrent transient response of the samples in a 0.2 M of
directing role of GO over CNT results in a more intimate Na2SO4 aqueous solution under visible light irradiation. Reprinted with
interfacial contact between GR and TiO2 (Fig. 14b–e), thus permission from ref. 78. Copyright 2011, American Chemical Society.

5800 | Nanoscale, 2012, 4, 5792–5813 This journal is ª The Royal Society of Chemistry 2012

Table 1 Samples composition, bandgap energy, rate constant k, and TICa for CO, CO2, and H2O of TiO2–graphene133
Sample Graphene/g Ebg/eV k (365 nm)/h
1 CO [TIC] CO2 [TIC]
TiPC0000 0 3.20 0.02686 4 7
TiPC0005 0.005 3.10 0.01350 10 18
TiPC0010 0.01 3.05 0.03689 4 4
TiPC0050 0.05 2.90 0.01357 4 15
TiPC0100 0.1 2.70 0.01991 58 28
TiPC0200 0.2 2.40 0.01245 6 20
TiPC0500 0.5 >2 0.01004 11 34
a
TIC: total ion current.
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
selectivity (90–100%). This work conceptually demonstrates how
to synthesize a more efficient GR–semiconductor photocatalyst
and the key importance of preparative methods in affecting the
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morphology of as-prepared GR–semiconductor nanocomposites
and their photocatalytic activity. Moreover, the comparison
between GR–TiO2 and CNT–TiO2 counterparts will promote an
in-depth fundamental understanding of the analogies and
differences between GR and CNTs in controlling the
morphology of GR (or CNT)–semiconductor nanocomposites
and enhancing the photocatalytic performance of a semi-
conductor. This seminal work is expected to open a new doorway
to exploit graphene–semiconductor composite materials as
photocatalysts in the field of selective organic synthesis under
mild conditions, which would further enrich the potential
applications related to graphene’s role in photocatalysis.
According to previous reports,78,169 a combined strategy has
recently been developed by our group to improve the photo-
catalytic performance of GR–TiO2 nanocomposites.182 We
found that the photoactivity of GR–TiO2 can be further
enhanced by decreasing defects of GR and increasing interfacial
contact between GR and semiconductor TiO2. As seen in
Fig. 15A–E, the solvent exfoliated graphene (SEG) with lower
defects can contact with TiO2 intimately, making more efficient
use of the electron conductivity of graphene, by which the life-
time and transfer of photoexcited charge carriers can be
improved more efficiently. Accordingly, compared with GR–
TiO2 and SEG–P25, SEG–TiO2 exhibits enhanced photo-
catalytic performance for selective oxidation of various alcohols
to the corresponding aldehydes under visible light irradiation at
ambient conditions, as exemplified in Fig. 15F and G. This work
highlights the key importance of rational fabrication and design
of GR–semiconductor nanocomposites with improved photo-
catalytic performance toward specific applications.
Besides TiO2, we have also studied another common semi-
conductor, CdS, to couple with GR. A series of cadmium sulfide–
graphene (CdS–GR) nanocomposites with different weight
addition ratios of GR have been synthesized via a facile one-step
solvothermal approach.79 It is found that, in the CdS–GR
nanocomposites, the CdS nanoparticles evenly overspread on the
graphene scaffold (Fig. 16A–C) and the introduction of GR
affects the morphology, optical and electronic nature of the
samples. Compared to blank-CdS obtained in the absence of
GR, CdS–GR exhibits enhanced photoactivity toward selective
oxidation of alcohols to their corresponding aldehydes under
ambient conditions, as reflected by two representative examples
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View Article Online
H2O H2O
[TIC] k (400 nm)/h
1 CO [TIC] CO2 [TIC] [TIC]
2 0.00959 7 8 2
4 0.00911 4 6 2
1 0.01317 5 7 1
4 0.00770 6 10 3
27 0.00530 36 15 3
3 0.00360 8 9 2
3 0.00527 5 5 2
in Fig. 16E and F. The high photoactivity of CdS–GR nano-
composites can be attributed to the integrative effect of the
enhanced light absorption intensity, high electron conductivity
of GR, and its significant influence on the morphology and
structure of the samples. A possible mechanism has been
proposed, as illustrated in Fig. 16D. Our results demonstrate that
graphene-based nanocomposites can serve as a type of promising
photocatalyst for selective organic transformations, which,
however, has not received adequate attention from the research
community. Therefore, it is hoped that our work could pave the
way for the exploration of GR-based semiconductor nano-
composites for visible-light-driven photocatalytic selective
organic transformations.
In addition to binary nanocomposites, very recently, we have
constructed ternary hybrids composed of CdS–GR–TiO2 on the
flatland of graphene oxide through an in situ strategy.183 As
displayed in Fig. 17A and B, the CdS nanoparticles carpet the
GR nanosheets evenly and the TiO2 nanoparticles decorate the
CdS–GR base foundation uniformly. The introduction of TiO2
has no effect on the morphology and porosity properties of the
samples, whereas it can enhance the photoactivity toward the
selective oxidation of alcohols to the corresponding aldehydes
under visible light illumination, as demonstrated in Fig. 17C. The
improved photocatalytic performance can be ascribed to the
combined interaction of the longer lifetime of photogenerated
electron–hole pairs, the faster interfacial charge transfer rate and
the larger surface area. As a proof-of-concept, this work
demonstrates that the careful design of GR–based composites by
coupling GR with multiple semiconductor compounds is favor-
able to the development of next generation photocatalyst systems
with improved photocatalytic capacity.
Besides photocatalytic selective oxidation processes, graphene-
based nanocomposites have been utilized in selective photore-
duction reactions. Hersam and coworkers169 have reported that
graphene–titania (P25) nanocomposites are active for photore-
duction of carbon dioxide (CO2) to methane (CH4) under UV
and visible light irradiation. They have produced graphene via
two different pathways, oxidation–reduction and solvent exfo-
liation, which are indicated as SRGO and SEG, respectively. It is
found that SEG–P25 nanocomposites exhibit a significantly
larger enhancement for photocatalytic reduction of CO2
compared to SRGO–P25, especially under visible light irradia-
tion (Fig. 18A). This can be ascribed to the fewer defects and
superior electrical mobility of SEG, implying a longer electronic
mean free path, which allows photoexcited electrons to diffuse
Nanoscale, 2012, 4, 5792–5813 | 5801
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Table 2 Selective oxidation of a range of alcohols over the TiO2–5% GR photocatalyst under the irradiation (l > 400 nm) of visible light for 20 h78

Entry Substrate Product Conv. (%) Yield (%) Sel. (%)

1 62 62 100

2 70 70 100

3 80 80 100
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4 74 73 99
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5 45 43 96

6 84 76 91

7 50 46 92

8 41 37 90

more effectively to reactive sites from the SEG–P25 interface,
thus decreasing the likelihood of their recombination with holes
on TiO2. The proposed mechanism is illustrated in Fig. 18B.
Upon illumination, the photoexcited electron is injected into the
graphene nanoplatelet, leaving behind a TiO2 confined hole. Due
to its lower density of defects, electrons in SEG are able to diffuse
farther, thus sampling a larger surface area for adsorbed CO2.
This work strongly suggests that a promising way to improve
graphene-based photocatalysts may benefit from careful
consideration of the electrical properties of the graphene
component.
More recently, noncovalently bound SEG–titania nanosheets
(TiNS) nanocomposites with low carbon defect densities have
been synthesized and utilized in photoreduction of CO2.187 As
shown in Fig. 19, the 2D-2D SEG–TiNS nanocomposites
demonstrate enhanced CO2 photoreduction activities under UV
excitation compared with 1D–2D single-walled carbon nano-
tubes (SWCNTs)–TiNS, which can be ascribed to the stronger
optoelectronic coupling between 2D–2D nanomaterials. The
results highlight the effects of nanomaterial dimensionality on
interfacial charge transfer and hence the photoactivity. This
work also motivates us to develop a reasonable system with an
identical contact degree of the carbon materials and the semi-
conductor, by which a reasonable comparison between semi-
conductor-carbon (GR, CNT) photocatalysts can be made.
In the light of the above studies it can be concluded that,
despite that photocatalytic processes are often regarded being
unselective, careful design of GR-based nanomaterials and
selection of proper reaction conditions make possible the effec-
tive utilization of these GR-based composite photocatalysts in
selective transformations, which provides a promising alternative
to more conventional synthetic pathways for synthesis of fine
chemicals.78,79,169,181–183,187
4. Photocatalytic hydrogen evolution
As the energy issues become increasingly serious worldwide, the
development of low-cost and efficient light-harvesting materials
has attracted increasing research interest for their great potential
to produce renewable energy sources. Hydrogen is regarded as
one of the ultimate clean fuels. The production of hydrogen with
a proper photocatalyst and solar power plays an important role
in clean and renewable energy systems not only because it is a
promising way of providing large-scale clean and renewable

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Fig. 15 (A) Raman spectra of graphene oxide (GO) and solvent-exfo-
liated graphene (SEG); photographs of (B) GO and (C) SEG dispersions
in water; (D) SEM image of TiO2–5% SEG nanocomposite; (E) photo-
current transient response of the samples in a 0.2 M of Na2SO4 aqueous
solution under visible light irradiation; photocatalytic selective oxidation
of (F) benzyl alcohol and (G) 3-methyl-2-buten-1-ol to corresponding
aldehydes over the nanocomposites of TiO2–5% SEG, TiO2–5% GR,
P25–1% SEG and P25–1% GR under visible light irradiation (l > 400
nm) of 4 h at room temperature. Reprinted with permission from ref. 182.
Copyright 2012, Royal Society of Chemistry.
Fig. 16 (A) SEM, (B) TEM, and (C) HRTEM images of the as-prepared CdS–5% GR (the inset of C is the SAED pattern); (D) schematic diagram of
the proposed mechanism for selective oxidation of alcohols to the corresponding aldehydes over the CdS–GR nanocomposite under visible light
irradiation; time-online photocatalytic selective oxidation of (E) benzyl alcohol and (F) cinnamyl alcohol to aldehydes over blank-CdS and CdS–5% GR
nanocomposite under the irradiation of visible light (l > 420 nm) under ambient conditions. Reprinted with permission from ref. 79. Copyright 2011,
American Chemical Society.
This journal is ª The Royal Society of Chemistry 2012
View Article Online
hydrogen, but also it could avert probable problems associated
with energy storage.190–192 Photocatalytic water splitting is one of
the most convenient approaches in this regard.193 Thus far, some
graphene-based nanocomposites have been utilized for photo-
catalytic water splitting.175,194–220
Amal’s group has prepared graphene–semiconductor nano-
composites via a photocatalytic reduction process, including
RGO–TiO2, RGO–WO3, RGO–BiVO4 and RGO–Ru/
SrTiO3.205,207,221 Their photoelectrochemical properties and
applications in water splitting have been studied. For example,
BiVO4–RGO has been synthesized by incorporating BiVO4 with
RGO using a facile single-step photocatalytic reduction, and the
typical SEM image is shown in Fig. 20A.205 Under visible light
illumination, a steady evolution of H2 and O2 can be obtained
and quantified on BiVO4–RGO at the rate of 0.75 and 0.21 mmol
h
1, respectively, whereas negligible gas production is observed
in the pure BiVO4 cell. This improvement of photocatalytic water
splitting is attributed to the longer electron lifetime of excited
BiVO4 as the electrons are injected to RGO instantly at the site of
generation, leading to a minimized charge recombination and the
improved contact between BiVO4 particles and transparent
conducting electrode RGO scaffold, as reflected in Fig. 20B and
C. Recently, they have developed an ingenious Z-scheme pho-
tocatalysis system for water splitting under visible light irradia-
tion.207 Mixtures of photoreduced graphene oxide (PRGO) with
BiVO4 (PRGO/BiVO4) and Ru/SrTiO3:Rh (PRGO/Ru/
SrTiO3:Rh) are prepared by photocatalytic reduction of GO on
BiVO4 and Ru/SrTiO3:Rh, respectively, under visible light illu-
mination in the presence of methanol as a hole scavenger
(Fig. 21A). In this system, PRGO functions as a solid-state
electron mediator, transferring the electrons from the conduction
band of BiVO4 to the vacancies in the impurity levels of Ru/
SrTiO3:Rh. The electrons in Ru/SrTiO3:Rh reduce water to H2
on the Ru cocatalyst, while the holes in BiVO4 oxidize water to
O2, accomplishing a complete water splitting cycle, as shown in
Fig. 21B. The time courses of H2 and O2 evolution indicates that
Nanoscale, 2012, 4, 5792–5813 | 5803

Fig. 17 (A) SEM and (B) TEM images of the as-prepared CdS–5% GR–10% TiO2 nanocomposite (the panels below are the elemental mapping patterns
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
of the boxed area of A); (C) time-online photocatalytic selective oxidation of benzyl alcohol to benzaldehyde over CdS–5% GR and CdS–5% GR–10%
TiO2 nanocomposites under the irradiation of visible light (l > 420 nm) at ambient conditions. Reprinted with permission from ref. 183. Copyright 2012,
American Chemical Society.
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Fig. 18 (A) Photocatalytic activity of SEG–P25 and SRGO–P25
nanocomposites for CO2 photoreduction under UV (l ¼ 365 nm) and
visible light illumination (l > 400 nm); (B) the proposed photocatalytic
mechanism for graphene–TiO2 nanocomposites. The color scheme is:
carbon (gray), hydrogen (white), oxygen (red), and titanium (blue), hole
(green). Reprinted with permission from ref. 169. Copyright 2011,
American Chemical Society.
this system is stable after the second cycle (Fig. 21C). This
significant work has opened a new doorway for the use of gra-
phene in the design of new and efficient systems for water
splitting.
A new type of composite containing graphene–Pt and
nitrogen-doped tantalite (Sr2Ta2O7
xNx) has been fabricated by
mixing graphene–Pt with Sr2Ta2O7
xNx, as shown in Fig. 22a.209
It is clear to see that the total amounts of generated hydrogen
during a testing course of over 4 h suggest the good stability of
the composite photocatalysts (Fig. 22c). The composite with an
optimal ratio exhibits a ca. 80% and 177% increase in the
hydrogen production compared to Sr2Ta2O7
xNx and undoped
Sr2Ta2O7, respectively, as displayed in Fig. 22d. In this system,
graphene serves as a scaffold and charge carrier transport
‘‘highway’’ to shuttle electrons to the platinum cocatalysts,
mitigating the recombination of charge carriers and facilitating
the electron transfer to photocatalyst surfaces for hydrogen
production reaction, as schematically illustrated in Fig. 22b. This
5804 | Nanoscale, 2012, 4, 5792–5813
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Fig. 19 The SEM images of (A) 1 wt% SWCNT–TiNS and (B) 1 wt%
SEG–TiNS nanocomposites (the inset is the corresponding schematic);
(C) photocatalytic activity of SWCNT–TiNS and SEG–TiNS for CO2
reduction to CH4 under UV and visible light irradiation. Reprinted with
permission from ref. 187. Copyright 2012, American Chemical Society.
strategic combination of nitrogen doping and the use of a
conductive electron transport ‘‘highway’’ makes possible further
improvement of the hydrogen production efficiency and provides
a new, promising approach to enhance the performance of
photocatalysts.
Fan et al.210 have prepared TiO2–reduced graphene oxide
(P25–RGO) nanocomposites through several techniques,
including UV-assisted photocatalytic reduction, hydrazine
reduction, and hydrothermal methods. For comparison, tita-
nium dioxide–carbon nanotubes (P25–CNTs) composites have
also been synthesized via a hydrothermal approach. Their pho-
tocatalytic activities are evaluated by the evolution of hydrogen
from alcohol solution under UV-vis irradiation. These results
demonstrate that the P25–RGO composites prepared by all of
the three methods exhibit significantly higher rates of H2 evolu-
tion than P25 alone. Among the P25–RGO composites, the P25–
RGO-hydrothermal composite affords the highest rate of H2
evolution, which is also higher than that over P25–CNT catalyst
(Fig. 23). They have proposed that the intimate contact between
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 View Article Online

Fig. 20 (A) SEM image of BiVO4–RGO; (B) visible light voltage–photocurrent functions of BiVO4, BiVO4–RGO, and TiO2 (under UV irradiation);
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

(C) illustration of photocatalytic water splitting in a photoelectrochemical cell based on BiVO4–RGO. Reprinted with permission from ref. 205.
Copyright 2010, American Chemical Society.
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Fig. 21 (A) SEM image of (Ru/SrTiO3:Rh)–(PRGO/BiVO4); (B) illustration of water splitting mechanism in a Z-scheme photocatalysis (Ru/
SrTiO3:Rh)–(PRGO/BiVO4) system under visible light irradiation; (C) overall water splitting under visible light irradiation (l > 420 nm) by the (Ru/
SrTiO3:Rh)–(PRGO/BiVO4) system. Reprinted with permission from ref. 207. Copyright 2011, American Chemical Society.

Fig. 22 (a) TEM image of graphene–Sr2Ta2O7
xNx; (b) schematic diagram for charge carrier separation and photocatalytic H2 production on Pt-
loaded graphene–Sr2Ta2O7
xNx photocatalyst under simulated solar light irradiation; (c) hydrogen evolution rates in the course of 4.5 h using a 300 W
Xe lamp and (d) hydrogen evolution rate (per hour) of various photocatalysts. Reprinted with permission from ref. 209. Copyright 2011, American
Chemical Society.

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P25 and RGO may accelerate the transfer of photogenerated
electrons on P25 to RGO, suppressing the recombination of
charge carriers. However, using semiconductor solid particles
may not make good use of the structural advantages of GR/GO,
thus leading to an unsatisfactory contact between the semi-
conductor particles and GR sheets. Therefore, more efficient
preparation methods are expected to give a further improvement
of photoactivity of GR-based photocatalysts for water splitting.
CdS-cluster-decorated graphene nanosheets have been fabri-
cated through a solvothermal method, as shown in Fig. 24a,
which can be used as an efficient visible-light-driven photo-
catalyst for hydrogen production.211 It was found that graphene
nanosheets in the composite could enhance the crystallinity and
the specific surface area of CdS clusters. An appropriate amount
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
of graphene can dramatically improve the photocatalytic
activity. The optimal weight percentage of graphene is found to
be 1.0 wt%, which results in a high visible-light photocatalytic H2
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production rate of 1.12 mmol h
1 with 0.5 wt% Pt as a cocatalyst,
as displayed in Fig. 24b. The proposed mechanism is illustrated
Fig. 23 (a) TEM image of P25–RGO-hydrothermal (P25/RGO ¼ 1/0.2);
(b) comparison of photocatalytic performances of P25, P25–CNT
composites with different mass ratios of P25/CNT, and P25–RGO
composites (mass ratio of P25/RGO ¼ 1/0.2) prepared by different
methods for the evolution of H2 from methanol aqueous solution using a
200 W Xe arc lamp. Reprinted with permission from ref. 210. Copyright
2011, American Chemical Society.
Fig. 24 (a) TEM image of sample CdS–1% GR (denoted as GC1.0); (b) comparison of the visible light photocatalytic activity of samples GC0, GC0.5,
GC1.0, GC2.5, GC5.0, GC40, and G for H2 production using 10 vol% lactic acid aqueous solution as a sacrificial reagent and 0.5 wt% Pt as a cocatalyst
(l > 420 nm); (c) schematic illustration of the charge separation and transfer in the graphene–CdS system under visible light irradiation. Reprinted with
permission from ref. 211. Copyright 2011, American Chemical Society.
5806 | Nanoscale, 2012, 4, 5792–5813
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in Fig. 24c. The photoexcited electrons transfer from the
conduction band of semiconductor CdS not only to the located
Pt, but also to the carbon atoms on the graphene sheets, which
are accessible to protons that could readily transform to H2. This
work demonstrates that the unique features of graphene enable it
to be an excellent supporting material for semiconductor nano-
particles as well as an excellent electron collector and transporter
to separate photogenerated electron–hole pairs.
In addition to the utilization of pristine graphene, N-doped
graphene (N-graphene) has also been prepared to couple with
CdS nanocomposites for hydrogen production from water under
visible light irradiation (Fig. 25a).212 The results, as displayed in
Fig. 25b, demonstrate that N-graphene/CdS nanocomposites
had a higher photocatalytic activity than pure CdS, which could
be attributed to the decreased recombination of the photo-
generated electron–hole pairs in the presence of N-graphene.
Moreover, the N-graphene/CdS photocatalyst shows no deacti-
vation for H2 evolution for longer than 30 h reaction time,
indicating that the cocatalyst of N-graphene as a protective layer
prevents CdS from photocorrosion under light irradiation
(Fig. 25c). Thus, N-doped graphene could serve as a protective
material for semiconductors, promoting potential application for
hydrogen production by using solar energy.
More recently, Xiang et al.213 have fabricated a ternary
composite material consisting of TiO2 nanocrystals grown in the
presence of a layered MoS2/graphene (MG) hybrid as a high-
performance photocatalyst for H2 evolution by a two-step simple
hydrothermal process, as shown in Fig. 26A. Even without a
noble-metal cocatalyst, the TiO2/MG composite containing 0.5
wt% MG cocatalyst with 95 wt% MoS2 and 5 wt% graphene
shows high photocatalytic H2 production activity with a rate as
high as 165.3 mmol h
1 under UV light irradiation (Fig. 26B).
The corresponding apparent quantum efficiency reaches 9.7% at
365 nm. This unusual photocatalytic activity arises from the
positive synergetic effect between MoS2 and graphene compo-
nents in this hybrid cocatalyst, which serve as an electron
collector and a source of active adsorptive sites, respectively, as
illustrated in Fig. 26C. This work also presents an inexpensive
noble metal free photocatalyst to achieve highly efficient H2
evolution.
This journal is ª The Royal Society of Chemistry 2012
 View Article Online

Fig. 25 (a) HRTEM image of N-graphene (2 wt%)/CdS photocatalyst; (b) H2 evolution of CdS, N-graphene/CdS composites with different contents of
N-graphene (l > 420 nm); (c) a typical time course of hydrogen yield over N-graphene/CdS, six runs in one continuous reaction. Reprinted with
permission from ref. 212. Copyright 2011, American Chemical Society.
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
Downloaded by Stanford University on 02/04/2013 04:26:24.

Fig. 26 (A) TEM image of T/95M0.5G composite; (B) photocatalytic H2 evolution of TiO2/MG composites under UV light irradiation (l ¼ 365 nm);
(C) schematic illustration of the charge transfer in TiO2/MG composites. Reprinted with permission from ref. 213. Copyright 2012, American Chemical
Society.

Besides the particles-on-a-sheet geometry of graphene-based interaction with the photogenerated holes in the valence band of
nanocomposites, TiO2@nanographene oxide (NGO) core–shell GO can avoid electron–hole recombination. Besides, they found
structure (NGOTs) has been reported by Choi’s group, as shown that a cocatalyst, such as Pt, is not essential for steady H2
in Fig. 27a and b.215 Compared with reduced GO/TiO2, con-
sisting of TiO2 nanoparticles loaded on a larger graphene sheet
(r-LGOT), the reduced NGOTs (r-NGOTs) exhibit higher
activity for photocatalytic H2 production under UV irradiation
(l > 320 nm), which is ascribed to the better contact between
the r-GO shell and TiO2 (Fig. 27c). This study indicates that the
geometry of the core/shell structure could be effective in the
design of a graphene/TiO2 composite for solar energy conversion
applications.
Besides graphene-based nanocomposites, graphite oxide might
be able to become a next generation photocatalyst.216,222 Yeh
et al.216 have reported that graphite oxide (GO) at an appropri-
ately oxidized level can serve as a photocatalyst for stable H2
generation from water in an aqueous solution or pure water
under UV or visible light irradiation. In GO (Fig. 28a), the
conduction band edge, which is mainly formed by the anti-
bonding p* orbital, has a higher energy level than that needed for
H2 generation, thus leading to electron injection into the solution
phase for H2 generation. The results in Fig. 28b and c indicate
that the total evolution of H2 from the aqueous methanol solu- Fig. 27 (a) TEM and (b) HRTEM images of r-NGOT-0.7; (c) illustra-
tion after 6 h irradiation is ca. 17 000 mmol, which far exceeds the tion of the preparation procedure of r-NGOT and r-LGOT and the
amount of hydrogen obtained from pure water (ca. 280 mmol). photocatalytic production of hydrogen in the aqueous suspension of
This difference can be ascribed to the role of methanol as a TiO2, r-LGOT, and r-NGOT (l > 320 nm). Reprinted with permission
sacrificial hole scavenger, which means that the effective from ref. 215. Copyright 2012, American Chemical Society.

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Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
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Fig. 28 (a) TEM image of GO wrinkled sheets; time course of H2 evolution from a 20 vol% aqueous methanol solution (MeOH/water) or pure water
with suspended photocatalysts under (b) mercury-lamp irradiation and (c) visible light irradiation (l > 400 nm); (d) schematic energy-level diagram of
GO relative to the levels for H2 and O2 generation from water. Reprinted with permission from ref. 216. Copyright 2010, John Wiley & Sons, Inc.
production from water using GO photocatalyst. The corre-
sponding mechanism is also proposed, as illustrated in Fig. 28d.
Efficient H2 generation on GO can be attributed to the fact that
GO sheets are molecule-like and highly dispersed in water and
the carbon atoms on the sheets are therefore accessible to
protons that can readily transform to H2 by accepting photo-
generated electrons from the carbon atoms. This work demon-
strates the potential of graphitic materials as a medium for water
splitting under solar illumination.
5. Future perspectives
In this updated review, the current status of applications of
graphene (GR)-based nanocomposites for photocatalytic
processes have been summarized, including nonselective
processes for degradation of pollutants, selective organic trans-
formations for synthesis of fine chemicals and water splitting to
clean hydrogen energy. It is clear that GR-based materials can
serve as a new family of promising photocatalysts. The intro-
duction of GR into various semiconductor photocatalysts as well
as metal nanoparticles can improve the photocatalytic perfor-
mance of semiconductors or metal nanoparticles owing to the
extended light absorption range, high adsorption capacity,
specific surface area and superior electron conductivity of GR.
Undoubtedly, the promising opportunities offered by GR are
outstanding. However, some existing challenges merit attention
in order to achieve more efficient GR-based photocatalysts. In
other words, some fundamental and essential issues are still
unaddressed. For instance, as discussed in previous
reviews,12,16,45,46,48,223 the underlying mechanisms of GR-based
materials applied in energy related systems are not fully under-
stood and careful designs of the functional composites are
required to achieve more efficient performance. In fact, in
addition to these problems, there are other challenges in this
5808 | Nanoscale, 2012, 4, 5792–5813
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regard, which have not been brought into special focus so far. To
realize these challenges is of great importance for further devel-
opment of GR-based nanocomposites for photocatalytic appli-
cations in a more rational manner.
Firstly, a thoughtful and necessary comparison among GR
and its carbon allotropes e.g., CNT, C60 and activated carbon,
which is often neglected in the literature, ought to be carried out
in order to better understand the essential advantages of GR and
make use of it more reasonably and efficiently.106,146 Recalling the
history of carbon materials, it should be noted that the discovery
of C60 and CNT gave rise to a huge research upsurge at one
time224–227 and recent years have seen a quite same phenomenon
caused by the emergence of GR. Before the research interest in
synthesis of GR-based composite photocatalysts, a large body of
research works regarding CNT-, C60- and activated carbon-
based photocatalysts have also been reported in literature.146,228
In view of these facts, we wonder since the functions of carbon
materials lie in their chemical inertness, high adsorption capacity
and excellent charge mobilities,46 is GR different from other
carbon allotropes in essence and what is the substantial advan-
tages of GR over its forbears? Our group15,78 has carried out
some preliminary studies in this intriguing aspect. Taking CNT–
P25 as an example and degradation of pollutants as model
reactions, we found that the key features for GR–P25, including
enhancement of adsorptivity of pollutants, light absorption
intensity, electron–hole pairs lifetime, extended light absorption
range and decreased photocatalytic activity with high content of
GR, can also be observed in the composite of CNT–P25.15
Considering the unique structural property of graphene oxide
(GO), the precursor of GR, we improved the synthesis approach
by using ‘‘soft’’ integration which leads to an intimate interfacial
contact between TiO2 and GR. In order to harness the electron
conductivity of GR efficiently, one should utilize the superior
and easily accessible ‘‘structure-directing’’ role of GO. Compared
This journal is ª The Royal Society of Chemistry 2012

with the CNT–TiO2 counterpart, GR–TiO2 exhibits a much
more active visible light photocatalytic activity toward selective
oxidation of alcohols to aldehydes. Our results indicate that
more efficient GR–semiconductor photocatalysts can be devel-
oped through rational design and engineering of the GR surface
with semiconductor ingredients. Our comparison study suggests
that it is inevitable to draw a comparison amongst the carbon
materials (GR, CNT, C60 and activated carbon) to get answers to
the above questions and, thus, enable GR to play its part better
in improving the photocatalytic performance of semiconductors.
More recently, Ye et al.175 have reported that the CdS–GR
nanocomposites with an optimized mass ratio exhibit higher
photocatalytic activities than the CdS–CNT counterpart for both
the evolution of hydrogen and the degradation of methyl orange
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
under visible light irradiation, which is ascribed to the stronger
interaction or larger contact interface between CdS and GR.
However, there are still fundamental questions worthy of further
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study. For example, if we prepare GR–semiconductor and CNT–
semiconductor nanocomposites which both feature intimate
interfacial contact in a similar way, how different is their pho-
toactivity? Currently, our group is actively carrying out studies in
this regard.
Secondly and notably, one of the most common approaches
reported in the literature to prepare GR-based nanocomposites is
based on the dispersion of semiconductor solid particles, which
refers to ‘‘hard’’ integration, on the surface of GR nanosheets.
Such a strategy introduces GR merely for the sake of GR itself
without putting it into full play with elaborate design and is unable
to utilize the structural advantage of 2D GR.78 Consequently, a
quite poor interfacial contact between the semiconductor and GR
scaffold is often obtained. Since one of the key roles of GR in the
GR-based composite photocatalysts is to transfer the photo-
generated electrons, an unsatisfactory interfacial contact is not
propitious for GR to play its role, and will weaken the synergetic
effect of GR and photoactive semiconductor and diminish the
photocatalytic performance of the GR-based photocatalysts.
Given this issue, the development of more efficient synthesis
methods or strategies is much more desirable to make full use of
the structural and electronic merits of GR for achieving improved,
superior photocatalytic performance.
Thirdly, as mentioned above, there is room to improve the
interfacial contact between GR and semiconductor components
in GR-semiconductor photocatalysts in order to improve the
overall photocatalytic performance. However, this significant
issue is not just a problem of tighter connection between each
respective component in GR-based composite photocatalysts,
but also about optimization of the atomic charge transfer path
from the different respective components materials, which
probably needs to involve band bending calculations. In addi-
tion, some interfacial mediators, possibly transition metal ions or
metal nanoparticles, could help optimize the charge transfer in
the interface of GR-based composite photocatalysts. In this
regard, besides the experimental efforts, theoretical calculations
on the interfacial band composition and regulation should be
paid attention. A joint effort between experiment and theory
would significantly advance our in-depth insight into the
microscopic charge transfer pathway for GR-based photo-
catalysts, which in turn offers a guide towards the design target
of smarter GR-based photocatalysts for potential applications.
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View Article Online
Fourthly, the approaches for producing GR need to be
improved with more work on the preparation of GR or graphene
oxide (GO) sheets with high quality, such as high purity, few
defects, controlled size, lateral area and shape. So far, one of the
most commonly used methods to produce GR is the strong
oxidative exfoliation of graphite in a solution phase (GO is
obtained by this step) followed by chemical reduction of GO.
Although this approach is effective for mass production of GR, it
inevitably produces a large number of defects in the GR nano-
sheets due to the change in its aromatic structure and the
formation of oxygen-containing groups, which could diminish
the electrical conductivity and mechanical strength of GR,
thereby deteriorating the photocatalytic performance of the GR-
based nanocomposites. Although most of the functional groups
can be removed by the reduction procedure, only partial resto-
ration of the sp2-conjugated graphene network can be achieved.
Banhart et al.229 have reported that some of the predicted
extraordinary properties of GR can only be observed at an
extremely low defect concentration. The defects strongly affect
the electronic, optical, thermal and mechanical properties of GR;
besides, each defect has a certain mobility parallel to the GR
plane which weakens the ability of GR sheets in the transport of
electrons. The results obtained by Hersam’s group demonstrate
the effects of defects on the photocatalytic performance of GR.169
They found that the nanocomposites based on the less defective
solvent-exfoliated graphene (SEG) exhibit significant enhanced
photocatalytic activity compared to that of solvent-reduced
graphene oxide (SRGO), which is due to the superior electrical
mobility of SEG. Thus far, studies on the production of high-
quality GR are scarce.169 Therefore, the production of large-scale
GR sheets with minimal defects or oxidation sites, particularly
with controlled size and shape, is still challenging and significant
for practical applications.
Fifthly, it is necessary to clarify that a single GR nanosheet is
the standard form of GR and the superior properties of GR are
associated with an individual sheet, such as the extremely large
specific surface area and optical transparency. However, due to
the strong cohesive van der Waals energy of the p-stacked layers
in graphite and the high surface area of GR, the GR or GO tends
to undergo irreversible agglomeration, being present in the multi-
layer form. Notably, when the layer number is fewer than 10, GR
properties vary as a function of layer number and interlayer
ordering.4 For example, single-layer GR is a zero-gap semi-
conductor with a linear energy dispersion so that its charge
carriers can be viewed as massless particles that travel at an
effective speed of 106 m s
1. Bilayer GR is likewise a zero-gap
semiconductor whose electrons obey a parabolic energy disper-
sion. A tunable bandgap of several hundred meV can be induced
in bilayer GR by breaking the symmetry between the two GR
layers by carefully applying a gate bias.230 As for trilayer GR, it is
a semi-metal with a band overlap that can be controlled by an
external electric field.231 Despite the recent burst of activity on the
production of GR, comparatively little progress has been made
toward the generation of GR with tailored thickness, lateral area,
size and shape.4 Therefore, in order to further improve and
exploit the performance of GR and GR-based composite pho-
tocatalysts, the precise definition and synthesis of free-standing
GR must be taken into account and paid sufficient attention.
Notably, the stacking of GR has been observed widely for
Nanoscale, 2012, 4, 5792–5813 | 5809

research works regarding GR-based photocatalysts in literature
so far.15,78,79,104–177,194–220 Thus, it is a challenging but significant
task for the synthesis of GR-based photocatalysts in which the
present form of GR remains as a single GR nanosheet. If this
technical challenge can be overcome, perhaps, the full superlative
potential of GR as always claimed in literature could be released
to the maximum.
Finally, the reported GR-based nanocomposite photocatalysts
are mostly focused on binary components. In other words, GR is
only coupled with another single compound. Considering that
the main force behind the rapid development of the GR-based
nanocomposites is the aspiration to combine the favorable
properties of GR with other constituent nanomaterials,12 there-
fore, beyond binary hybrid systems, the multi-component GR-
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K
based hybrid nanostructures may provide new insight into the
development of novel 3D nanoarchitectures with versatile and
extraordinary properties and applications. For instance, Kamat
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and coworkers232 have observed a remarkably high photocurrent
generation in a organic/inorganic ternary composites of
porphyrin, ZnO nanoparticles and reduced graphene oxide as a
hierarchical electron transfer cascade system. This pioneering
research work suggests that more efforts should be devoted to
preparing the multi-component GR-based nanocomposites for
better performance and wider applications instead of getting
stuck in binary composites.
Undoubtedly, GR-based nanocomposites hold a great poten-
tial for being robust materials to address various environmental
and energy-related issues. In spite of the remarkably rapid
progress, the ability of GR nanosheets in this field has yet to be
exploited fully. The research field of GR-based photocatalysts is
still very young. Opportunities as well as challenges exist together
for the development of GR-based multifunctional photocatalytic
systems. With the reasonable design and full exploration of
graphene’s potential, the applications of GR-based composite
photocatalysts for conversion of solar to chemical energy would
significantly be enriched in a more rational way. The intense and
rational efforts from the union between academia and industry
would open a revolution of clean and renewable energy by
utilizing GR-based composite materials, which we believe will be
far beyond what has been reported in this review paper.
Acknowledgements
The support by the National Natural Science Foundation of
China (NSFC) (20903023, 21173045), the Award Program for
Minjiang Scholar Professorship, the Natural Science Foundation
(NSF) of Fujian Province for Distinguished Young Investigator
Grant (2012J06003), Program for Changjiang Scholars and
Innovative Research Team in Universities (PCSIRT0818),
Program for Returned High-Level Overseas Chinese Scholars of
Fujian province, and the Project Sponsored by the Scientific
Research Foundation for the Returned Overseas Chinese
Scholars, State Education Ministry, is gratefully acknowledged.
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