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Cite this: Nanoscale, 2012, 4, 5792


www.rsc.org/nanoscale REVIEW
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’’.

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
State Key Laboratory Breeding Base of Photocatalysis, College of sheets of carbon atoms—graphene (GR).1,2 GR, as an allotrope
Chemistry and Chemical Engineering, Fuzhou University, Fuzhou
350002, Fujian, P.R. China. E-mail: yjxu@fzu.edu.cn; Fax: +86 591 of carbon, is composed of layers of carbon atoms packed into a
83779326; Tel: +86 591 83779326 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 Fujian, P. R. China in 1986. He
received her bachelor degree in received his bachelor degree in
chemical engineering & tech- applied chemistry from
nology from East China Insti- Zhangzhou Normal University
tute of Technology (2009), P. (2009), P. R. China. Currently,
R. China. Currently, she is he is pursuing his PhD degree
pursuing her PhD degree with with the supervision of Prof. Xu
the supervision of Prof. Xu at at National Research Center for
the National Research Center Environmental Photocatalysis
for Environmental Photo- Engineering and Technology,
catalysis Engineering and Tech- Fujian Provincial Key Labora-
nology, Fujian Provincial Key tory of Photocatalysis-State
Nan Zhang Laboratory of Photocatalysis- Yanhui Zhang Key Laboratory Breeding Base,
State Key Laboratory Breeding College of Chemistry and
Base, College of Chemistry and Chemical Engineering, Fuzhou
Chemical Engineering, Fuzhou University, P. R. China. Her main University, P.R. China. His main research interests include the
research interests include the fabrication of core–shell and carbon- synthesis of nanostructured materials, especially graphene-based
based nanocomposites for potential target applications in hetero- composites nanomaterials for applications in heterogeneous
geneous photocatalysis. photocatalysis.

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using different approaches, including thermal exfoliation, inability to utilize visible light, insufficient quantum efficiency, or
mechanical cleavage, chemical vapor deposition, and chemical the possible photodegradation of the catalyst. Designing novel
functionalization.3–10 Recent years have witnessed a cornucopia catalysts to meet these technical needs is still a challenge. Due to
of approaches toward the exploration of GR, this sparkling its unique atom-thick 2D structure, excellent transparency, high
rising star on the horizon of material science.11–13 Considering its specific surface area, locally conjugated aromatic system, supe-
planar state, GR can be wrapped up into zero-dimensional rior electron mobility, and high chemical, electrochemical
spherical fullerenes with the introduction of pentagons, rolled stability, GR is regarded as an ideal high performance candidate
along a given direction into one-dimensional carbon nanotubes for photocatalyst carriers or promoter.46 That is, to synthesize
or staked into three-dimensional graphite.1 Hence, GR is GR-based nanocomposites toward specific photocatalytic reac-
recognized as the basic building block of all-dimensional carbon tion opens up a new promising pathway for the further devel-
materials. Its lamellar structure bestows remarkable and unique opment of photocatalysis.
properties, such as a high mobility of charge carriers (>200 000 It is undoubted that the discovery of GR brings about enor-
cm2 V1 s1 at electron densities of 2  1011 cm2), exceptional mous opportunities for science and technology. Although there
Young’s modulus values (1.0 TPa), large spring constants (1– have been vast numbers of reports on GR, including exploration
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

5 Nm1), theoretically high specific surface area (2630 m2 g1), of novel approaches to synthesize GR or GR-based nano-
excellent thermal conductivity (5000 Wm1 K1) and optical materials and their utilization,10,87–96 most of them typically
transmittance (97.7%),14 which have spurred enormous interest involve introduction of GR merely for the sake of GR itself via
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in the scientific and industrial communities. On account of its relatively simplistic methods such as mixing instead of putting it
favorable characteristics, GR has been utilized in diverse areas, into full play with elaborate design. The improvements seen with
such as nanoelectronics, optoelectronics, chemical and the optimization of preparation methods and making full use of
biochemical sensing, polymer composites, H2 production and GR are still unsatisfactory.45 Therefore, research attention
storage, intercalation materials, drug delivery, supercapacitors, should focus on how to utilize fully GR, rather than separately
catalysis and photovoltaics.15–62 imposing hype on the ‘miracle of GR’ in much the same way as
Among various topics, the fabrication of GR-based catalysts, its carbon forebears (fullerenes or carbon nanotubes), which
especially those for photocatalysis, is currently an important could significantly advance our rational fabrication of smart
issue of particular concern. In the 21st century, aggravating GR-based nanocomposites for various applications.78
energy and environmental problems such as pollution, fossil fuel This tutorial review aims to give a relatively systematic,
depletion and global warming are ringing the alarm bells for updated summary of the current status of GR-based nano-
human society.46 Photocatalysis has attracted intense attention composites applied in photocatalysis, including nonselective
during the past decades because of its potential for environ- degradation of pollutants, selective transformations for organic
mental purification and converting photon energy into chemical synthesis of fine chemicals and water splitting to clean hydrogen
energy.12,16 This green technology has been widely applied to energy. Notably, the application of GR-based nanocomposites
nonselective processes for the degradation of pollutants, selective in photocatalytic selective transformation is not covered by
organic transformations for synthesis of fine chemicals, water previous reviews.12,16,45,46,48 Furthermore, some challenges con-
splitting to hydrogen energy and other photoelectrochemical fronted by GR-based photocatalysts are discussed in the future
processes in both the gas and liquid phases.63–86 However, the perspectives section. It is hoped that this updated review would
practical applications of this technique are limited by the 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-
Prof. Yi-Jun Xu received his lished in Nature put it,97 GR is not a miracle material, just a very
PhD degree in heterogeneous promising one and it will take restraint and sustained interest to
catalysis at the School of deliver its potential. Although the hunt is on for applications that
Chemistry, Cardiff University, can exploit graphene’s remarkable properties, the research work
U.K. in 2006 with Prof. Graham necessary to find out how it could best be harnessed remains
J. Hutchings (FLSW FRS). relatively incomplete. Such targeting of graphene’s potential will
From 2007 to 2009, he worked be vital to its success including its application in photocatalysis.
as a postdoctoral fellow at the What we should do is to exploit its properties and applications in
Fritz Haber Institute of the Max a more reasonable and rational way instead of joining the gra-
Planck Society, Berlin, Ger- phene ‘‘gold rush’’.97
many. After that, he joined the
faculty as a Minjiang Scholar
2. Photocatalytic nonselective processes
Professor at Fuzhou University.
Yi-Jun Xu His current research interests Nonselective photocatalysis has been attracting research interest
are mainly focused on synthe- because of its great potential for environmental remediation,
sizing nanostructured materials, such as the removal of stubborn, noxious compounds or non-
such as graphene-based nanocomposites and core–shell nano- biodegradable molecules from air, soil and water.15,98–103 During
structured materials, and exploring their applications in the area of these nonselective processes, the contaminants are mineralized
heterogeneous photocatalysis. 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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Fig. 2 (A) Diffuse reflectance absorption spectra of P25–GR; (B)


results of photoactivities demonstrate that P25–GR exhibits
schematic structure of P25–GR and tentative processes of the photo-
enhanced activity toward the photodegradation of methylene blue degradation of MB over P25–GR; comparison of photocatalytic activity
(MB) compared to the bare P25 under both UV and visible light in the degradation of MB under (C) UV light (l ¼ 365 nm) and (D) visible
irradiation. Moreover, it also shows higher photodegradation light (l > 400 nm) over (1) P25, (2) P25–CNTs, and (3) P25–GR pho-
rate than the P25–CNTs with the same carbon content, as dis- tocatalysts. Reprinted with permission from ref. 109. Copyright 2010,
played in Fig. 2C and D, which can mainly be ascribed to the giant American Chemical Society.
2D planar structure, and enhancement of the adsorption of dyes
and of charge carrier transportation due to the addition of GR. performance is not taken into account. Consequently, it may be
The tentative processes of photodegradation of MB over P25–GR insufficient to conclude that the TiO2–graphene composite is
are illustrated in Fig. 2B. This work opens new possibilities in the essentially different from other TiO2–C (fullerene, carbon nano-
application of TiO2–carbon composites as photocatalysts for tube, or activated carbon) composites in enhancement of the
environmental protection. However, the effect of different weight photocatalytic activity of TiO2.15
addition ratios of carbon materials on the photocatalytic 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
Fig. 1 (A) Schematic illustration of selective catalysis at different sites TiO2 nanorods, the GO–TiO2 NRCs exhibit higher photocatalytic
on RGO as a 2-D conducting support, and (B) photographs showing the activity toward degradation of contaminant methylene blue (MB)
color changes observed during stepwise transfer of electrons: ① storing
and acid orange 7 (AO 7) under UV light irradiation.139,140
electrons in TiO2 by irradiating the deaerated ethanol suspension with
Obviously, the above research works all focus on simply
UV light (l > 300 nm) for 30 min; ② addition of deaerated ethanol
suspension of GO until no blue color remains (gray-colored solution random ‘‘hard’’ integration of pre-synthesized or commercially
results due to the formation of RGO); ③ reduction of Ag+ to Ag available semiconductor solids with GO sheets as also reported
nanoparticles (red color) by stored electrons in RGO following the in some other works.117–119,126,128,131,134,138 Such an ex situ
addition of deaerated AgNO3 solution. Reprinted with permission from hybridization makes pre-selection of nanostructures with desired
ref. 178. Copyright 2010, American Chemical Society. 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 For example, Du et al.148 have fabricated hierarchically
and non-uniform coverage of the particles on GR sheets and ordered macro-mesoporous TiO2–graphene composite films
poor interfacial contact between the semiconductors and GR, through a confinement self-assembly method. As illustrated in
which is unfavorable for GR to play its role during the photo- Fig. 4A, macro-mesoporous TiO2–graphene composite films are
catalytic processes.47,78 In contrast, an in situ crystallization prepared by adding graphene oxide (GO) to the system of
which allows the precursors of GR and metal compound to pre- colloidal crystals assembled from monodisperse polystyrene (PS)
mix together can mitigate these problems and result in a uniform spheres with controlled sizes and subsequently reducing GO in
coverage of nanocrystalline semiconductor nanoparticles on GR situ within the films. The obtained samples are designated as
sheets, thus favoring improvement of the photocatalytic (GR)–Ti–(Ma170/200)–Me, for which the presence of bracketed
performance. components depends on the preparation process. The diameter

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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
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

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
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Fig. 4 (A) Illustration for the preparation of a macro–mesoporous the most reactive facets with a high surface energy.179 There are
TiO2–graphene composite film; (B) typical SEM and (C) TEM micro- some studies on the nanocomposites consisted of anatase TiO2
graphs of a macro–mesoporous TiO2–graphene composite film assem- with exposed {001} high-energy facets and graphene.151,152,174 For
bled from 300-nm diameter polystyrene spheres; (D) photocatalytic instance, nano-sized anatase TiO2 sheets mainly dominated by
degradation of MB under UV light irradiation (l ¼ 365 nm) using (a) Ti– {001} facets have been prepared on graphene sheets (T–GS) via a
Me, (b) GR–Ti–Me, (c) Ti–Ma200–Me, (d) GR–Ti–Ma200–Me, (e) Ti– facile solvothermal route, as shown in Fig. 6A–D.152 In
Ma170–Me, and (f) GR–Ti–Ma170–Me films. Reprinted with permission comparison with commercial P25 and pure TiO2 nanosheets, the
from ref. 148. Copyright 2011, American Chemical Society. 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
of Ma170/200 replicated by the PS template spheres is ca. 240/300 charge anti-recombination of graphene and the high catalytic
nm, respectively. It can be seen from Fig. 4B and C that 3D activity of {001} facets. Such a unique structure and advanced
ordered macropores are formed. Due to the specific, hierarchical chemical constitution holds promise for environment remedia-
structure and the introduction of GR, these TiO2–GR films show tion and energy conversion such as solar cell and water splitting.

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 This journal is ª The Royal Society of Chemistry 2012
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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
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

in terms of Ag/AgX/GO (X ¼ Br, Cl) nanocomposites fabricated


via a water/oil system at room temperature has been reported by
Fig. 6 (A) Schematic flowchart of the formation of TiO2–graphene Zhu et al. (Fig. 8A and B).114 As shown in Fig. 8C and D, these
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nanosheets (T–GS); (B) schematic of tetrabutyl titanate grafted on the hybrids exhibit distinctly enhanced photoactivity for degradation
GO surface by chemisorption; (C and D) typical TEM images of of methyl orange (MO) pollutant under visible light irradiation
T–GS–6 h; (E) liquid-phase photocatalytic degradation of RhB under the due to the good adsorptive capacity of Ag/AgX/GO, the smaller
irradiation of visible light (l > 400 nm) and (F) photocatalytic degra- size of the Ag/AgX nanoparticles, the facilitated charge transfer,
dation reaction kinetics of RhB over P25, T–GS–6h and pure TiO2
and the suppressed recombination of electron–hole pairs in Ag/
nanosheets. Reprinted with permission from ref. 152. Copyright 2012,
AgX/GO. Subsequently, they found that Ag/AgBr/GO synthe-
Royal Society of Chemistry.
sized through an oil/water microemulsion displays a higher
photocatalytic activity than that of the corresponding Ag/AgBr/
Beyond the most studied photocatalyst TiO2, some attention GO nanomaterial obtained by a water/oil microemulsion for
has been devoted to other semiconductors coupled with gra- degradation of MO under sunlight irradiation, which can be
phene.108,113,117,119,126–128,135,145,153,156,157,173 For example, Zou ascribed to the higher surface content of Ag and the higher mole
et al.157 have prepared sandwich-like metal oxide/graphene/metal ratio of metallic Ag0 to Ag+ (Fig. 8E and F).115 Their investi-
oxide (MO/G/MO) heterostructures by a simple and general gations open up new possibilities for development of stable and
nanocrystal-seed-directed (NSD) hydrothermal route, which efficient GO-based plasmonic photocatalysts to utilize visible
realizes large-scale growth of nanorod arrays of various semi- light as an energy source.
conductor metal oxides, including TiO2, ZnO, MnO2, CuO, and In addition to the aforementioned examples, increasing
ZrO2 on both sides of flexible graphene sheets (Fig. 7a–f). They interest has also been devoted to fabricating graphene-based
found that in the NSD hydrothermal processes, the MO nano- nanocomposite photocatalysts by developing new synthetic
crystals seeded on the graphene sheet play a key role in growth of strategies, such as premodification of graphene sheets and
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. 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-
Fig. 7 (a) Schematic of the growth process of metal oxides nanorods on diation (l > 400 nm); (E) schematic explanation for the one-pot
both sides of graphene sheets by the NSD hydrothermal route; (b–f) SEM surfactant-assisted synthesis of Ag/AgBr-based nanostructures via an oil/
images of sandwich MO/G/MO heterostructures obtained by the NSD water (top panel) and a water/oil (bottom panel) microemulsion system;
hydrothermal route: (b) TiO2/G/TiO2, (c) ZnO/G/ZnO, (d) MnO2/G/ (F) photocatalytic activities of Ag/AgBr-based plasmonic photocatalysts
MnO2, (e) CuO/G/CuO, (f) ZrO2/G/ZrO2; (g) photocatalytic degradation for the photodegradation of MO under sunlight irradiation. Reprinted
of MB under UV/Vis irradiation with a 500 W Xe lamp. Reprinted with with permission from ref. 114 and 115. Copyright 2011, 2012, American
permission from ref. 157. Copyright 2011, John Wiley & Sons, Inc. Chemical Society.

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adopting aided techniques including electrostatic interaction, is schematically illustrated in Fig. 10j. Under visible light irra-
electrospinning, electrodeposition, chemical vapor deposition diation, the electron would transfer from the excited dye, RhB*,
(CVD) and ultrasonication.107,113,124,127,129,154,155,159,161 For to graphene. Since the work-functions of CNTs and Ni are much
instance, graphene oxide (GO)-wrapped amorphous TiO2 higher than graphene, the injected electron on graphene plane
nanoparticles (NPs) have been synthesized by co-assembly of can continuously transfer to the CNTs and Ni particles, spatially
positively charged TiO2 NPs with negatively charged GO separating the RhB_+ radical and the electron, thus effectively
nanosheets, as illustrated in Fig. 9A.124 The SEM images indicate decreasing electron accumulation. Such CNT–RGO composites
that bare amorphous TiO2 NPs are entirely wrapped by GO represent a new family of innovative carbon materials for visible-
nanosheets; after a hydrothermal treatment for the reduction of light-activated photocatalysis. Besides, they have prepared gold
GO to GR and the crystallization of amorphous TiO2 NPs, the or copper modified-graphene composite photocatalysts for dye
dense precursors turn into porous nanospheres having a hierar- degradation under visible light irradiation.129,161 As shown in
chical structure that consists of interconnected nanocrystals with Fig. 11, the graphene-based composites can possess enhanced
intact graphene nanosheets (Fig. 9B–D). These GR–TiO2 NPs visible light photoactivities for dye degradation and the corre-
exhibit enhanced photoactivity under visible light irradiation for sponding photocatalytic mechanism is also proposed.129,161
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

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- composites of ZnFe2O4–graphene (G), MnFe2O4–G and
trons from excited MB to TiO2 NPs through graphene nano- NiFe2O4–G have been prepared by Wang’s group.111,112,158
sheets (Fig. 9F). This new synthetic strategy could enable a tight Under visible light irradiation, these graphene-based composite
integration of functional semiconductor NPs and graphene photocatalysts are not only photoactive in degradation of
nanosheets for the synthesis of highly photoactive graphene- methylene blue (MB), but can also be separated easily, as dis-
based metal oxide hybrid materials. played in Fig. 12.
Zhao and coworkers121,129,159,161 have carried out a series of Besides the applications of graphene-based nanocomposites in
studies on utilization of graphene in photocatalytic nonselective the photodegradation of organic dyes in the liquid phase, they
processes. They pillared layered graphene oxide (GO) and have also been applied in the gas phase.15,133,169 Our group15 has
reduced graphene oxide (RGO) platelets with carbon nanotubes utilized TiO2–graphene nanocomposites for the photocatalytic
(CNTs) using the CVD method with acetonitrile as the carbon degradation of a volatile organic pollutant (VOC), benzene, in
source and nickel nanoparticles as the catalysts (Fig. 10a–g).159 the gas phase for the first time (Fig. 3a and b). We found that the
The composite materials with RGO layers pillared by CNTs P25–GR nanocomposites exhibit much higher activity and
form a robust three-dimensional porous structure of specific stability than the reference catalyst of bare P25. Afterwards,
surface as high as 352 m2 g1. The unique porous structure and nonstoichiometric TiO2–graphene nanocomposites have been
the excellent electron transfer properties of graphene provide the fabricated by thermal hydrolysis of a suspension of graphene
CNT-pillared RGO composites with an excellent visible light nanosheets and a titania–peroxo complex.133 The photoactivity is
photoactivity in the degradation of Rhodamine B (RhB), as assessed by the photodegradation of butane in the gas phase
shown in Fig. 10h and i. The proposed photocatalytic mechanism 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.

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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 irradiation.170 As shown in Fig. 13B, the sample irradiated for 4 h
highest photoactivity for gas-phase decomposition of butane exhibits the highest antibacterial activity and its activity is
under UV and visible light irradiation. An increasing content of improved by a factor of about 6 and 7.5 relative to the activity of
graphene will lower the photodegradation rate, which has also the annealed graphene oxide/TiO2 and the bare TiO2 thin film,
been observed for the gas-phase degradation of benzene over respectively. More recently, Akhavan’s group fabricated gra-
P25–GR nanocomposites reported by our group.15 phene–tungsten oxide (GR–WO3) composite thin films with
In addition, graphene-based nanocomposites have also been sheet-like surface morphology.171 The GR–WO3 composite thin
utilized in the photoinactivation of bacteria.140,170,171 The TiO2– films show an excellent visible light photocatalytic performance
graphene films (Fig. 13A) prepared via deposition of graphene in the photoinactivation of viruses as compared to WO3, which is
oxide platelets on TiO2 thin films followed by annealing and assigned to the formation of W–C and W–O–C bonds. Their
irradiation process have been used for photocatalytic degrada- results could provide useful information for controlling the
tion of E. coli bacteria in an aqueous solution under solar light 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 but in the dark, as a control sample. Reprinted with permission from ref.
MB under visible light irradiation with different catalysts (l > 420 nm) 170. Copyright 2009, American Chemical Society.
(the inset is the magnetic separation property of the nanocomposite).
Reprinted with permission from ref. 111 and 158 (Copyright 2012, 2011, leading to better separation of the photogenerated carriers
American Chemical Society) and from ref. 112 (Copyright 2012, John (Fig. 14f) over GR–TiO2 as compared to CNT–TiO2. From
Wiley & Sons, Inc). Table 2, it can be seen that TiO2–5% GR can photocatalyze a
range of benzylic alcohols and allylic alcohols to the corre-
work efficiently on the destruction of environmental bio-organ- sponding aldehydes under visible light irradiation with high
isms under solar light irradiation.171

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
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Table 1 Samples composition, bandgap energy, rate constant k, and TICa for CO, CO2, and H2O of TiO2–graphene133

H2O H2O
Sample Graphene/g Ebg/eV k (365 nm)/h1 CO [TIC] CO2 [TIC] [TIC] k (400 nm)/h1 CO [TIC] CO2 [TIC] [TIC]

TiPC0000 0 3.20 0.02686 4 7 2 0.00959 7 8 2


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

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

5802 | Nanoscale, 2012, 4, 5792–5813 This journal is ª The Royal Society of Chemistry 2012
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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
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

and quantified on BiVO4–RGO at the rate of 0.75 and 0.21 mmol


h1, respectively, whereas negligible gas production is observed
in the pure BiVO4 cell. This improvement of photocatalytic water
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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
Fig. 15 (A) Raman spectra of graphene oxide (GO) and solvent-exfo- BiVO4 (PRGO/BiVO4) and Ru/SrTiO3:Rh (PRGO/Ru/
liated graphene (SEG); photographs of (B) GO and (C) SEG dispersions SrTiO3:Rh) are prepared by photocatalytic reduction of GO on
in water; (D) SEM image of TiO2–5% SEG nanocomposite; (E) photo- BiVO4 and Ru/SrTiO3:Rh, respectively, under visible light illu-
current transient response of the samples in a 0.2 M of Na2SO4 aqueous mination in the presence of methanol as a hole scavenger
solution under visible light irradiation; photocatalytic selective oxidation (Fig. 21A). In this system, PRGO functions as a solid-state
of (F) benzyl alcohol and (G) 3-methyl-2-buten-1-ol to corresponding
electron mediator, transferring the electrons from the conduction
aldehydes over the nanocomposites of TiO2–5% SEG, TiO2–5% GR,
band of BiVO4 to the vacancies in the impurity levels of Ru/
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. SrTiO3:Rh. The electrons in Ru/SrTiO3:Rh reduce water to H2
Copyright 2012, Royal Society of Chemistry. 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

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.

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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 Fig. 19 The SEM images of (A) 1 wt% SWCNT–TiNS and (B) 1 wt%
visible light illumination (l > 400 nm); (B) the proposed photocatalytic SEG–TiNS nanocomposites (the inset is the corresponding schematic);
mechanism for graphene–TiO2 nanocomposites. The color scheme is: (C) photocatalytic activity of SWCNT–TiNS and SEG–TiNS for CO2
carbon (gray), hydrogen (white), oxygen (red), and titanium (blue), hole reduction to CH4 under UV and visible light irradiation. Reprinted with
(green). Reprinted with permission from ref. 169. Copyright 2011, permission from ref. 187. Copyright 2012, American Chemical Society.
American Chemical Society.

strategic combination of nitrogen doping and the use of a


this system is stable after the second cycle (Fig. 21C). This conductive electron transport ‘‘highway’’ makes possible further
significant work has opened a new doorway for the use of gra- improvement of the hydrogen production efficiency and provides
phene in the design of new and efficient systems for water a new, promising approach to enhance the performance of
splitting. photocatalysts.
A new type of composite containing graphene–Pt and Fan et al.210 have prepared TiO2–reduced graphene oxide
nitrogen-doped tantalite (Sr2Ta2O7xNx) has been fabricated by (P25–RGO) nanocomposites through several techniques,
mixing graphene–Pt with Sr2Ta2O7xNx, as shown in Fig. 22a.209 including UV-assisted photocatalytic reduction, hydrazine
It is clear to see that the total amounts of generated hydrogen reduction, and hydrothermal methods. For comparison, tita-
during a testing course of over 4 h suggest the good stability of nium dioxide–carbon nanotubes (P25–CNTs) composites have
the composite photocatalysts (Fig. 22c). The composite with an also been synthesized via a hydrothermal approach. Their pho-
optimal ratio exhibits a ca. 80% and 177% increase in the tocatalytic activities are evaluated by the evolution of hydrogen
hydrogen production compared to Sr2Ta2O7xNx and undoped from alcohol solution under UV-vis irradiation. These results
Sr2Ta2O7, respectively, as displayed in Fig. 22d. In this system, demonstrate that the P25–RGO composites prepared by all of
graphene serves as a scaffold and charge carrier transport the three methods exhibit significantly higher rates of H2 evolu-
‘‘highway’’ to shuttle electrons to the platinum cocatalysts, tion than P25 alone. Among the P25–RGO composites, the P25–
mitigating the recombination of charge carriers and facilitating RGO-hydrothermal composite affords the highest rate of H2
the electron transfer to photocatalyst surfaces for hydrogen evolution, which is also higher than that over P25–CNT catalyst
production reaction, as schematically illustrated in Fig. 22b. This (Fig. 23). They have proposed that the intimate contact between

5804 | Nanoscale, 2012, 4, 5792–5813 This journal is ª The Royal Society of Chemistry 2012
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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–Sr2Ta2O7xNx; (b) schematic diagram for charge carrier separation and photocatalytic H2 production on Pt-
loaded graphene–Sr2Ta2O7xNx 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 in Fig. 24c. The photoexcited electrons transfer from the
electrons on P25 to RGO, suppressing the recombination of conduction band of semiconductor CdS not only to the located
charge carriers. However, using semiconductor solid particles Pt, but also to the carbon atoms on the graphene sheets, which
may not make good use of the structural advantages of GR/GO, are accessible to protons that could readily transform to H2. This
thus leading to an unsatisfactory contact between the semi- work demonstrates that the unique features of graphene enable it
conductor particles and GR sheets. Therefore, more efficient to be an excellent supporting material for semiconductor nano-
preparation methods are expected to give a further improvement particles as well as an excellent electron collector and transporter
of photoactivity of GR-based photocatalysts for water splitting. to separate photogenerated electron–hole pairs.
CdS-cluster-decorated graphene nanosheets have been fabri- In addition to the utilization of pristine graphene, N-doped
cated through a solvothermal method, as shown in Fig. 24a, graphene (N-graphene) has also been prepared to couple with
which can be used as an efficient visible-light-driven photo- CdS nanocomposites for hydrogen production from water under
catalyst for hydrogen production.211 It was found that graphene visible light irradiation (Fig. 25a).212 The results, as displayed in
nanosheets in the composite could enhance the crystallinity and Fig. 25b, demonstrate that N-graphene/CdS nanocomposites
the specific surface area of CdS clusters. An appropriate amount had a higher photocatalytic activity than pure CdS, which could
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

of graphene can dramatically improve the photocatalytic be attributed to the decreased recombination of the photo-
activity. The optimal weight percentage of graphene is found to generated electron–hole pairs in the presence of N-graphene.
be 1.0 wt%, which results in a high visible-light photocatalytic H2 Moreover, the N-graphene/CdS photocatalyst shows no deacti-
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production rate of 1.12 mmol h1 with 0.5 wt% Pt as a cocatalyst, vation for H2 evolution for longer than 30 h reaction time,
as displayed in Fig. 24b. The proposed mechanism is illustrated 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 h1 under UV light irradiation (Fig. 26B).
The corresponding apparent quantum efficiency reaches 9.7% at
365 nm. This unusual photocatalytic activity arises from the
Fig. 23 (a) TEM image of P25–RGO-hydrothermal (P25/RGO ¼ 1/0.2);
(b) comparison of photocatalytic performances of P25, P25–CNT positive synergetic effect between MoS2 and graphene compo-
composites with different mass ratios of P25/CNT, and P25–RGO nents in this hybrid cocatalyst, which serve as an electron
composites (mass ratio of P25/RGO ¼ 1/0.2) prepared by different collector and a source of active adsorptive sites, respectively, as
methods for the evolution of H2 from methanol aqueous solution using a illustrated in Fig. 26C. This work also presents an inexpensive
200 W Xe arc lamp. Reprinted with permission from ref. 210. Copyright noble metal free photocatalyst to achieve highly efficient H2
2011, American Chemical Society. evolution.

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 This journal is ª The Royal Society of Chemistry 2012
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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.
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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.

This journal is ª The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 5792–5813 | 5807
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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- regard, which have not been brought into special focus so far. To
sponding mechanism is also proposed, as illustrated in Fig. 28d. realize these challenges is of great importance for further devel-
Efficient H2 generation on GO can be attributed to the fact that opment of GR-based nanocomposites for photocatalytic appli-
GO sheets are molecule-like and highly dispersed in water and cations in a more rational manner.
the carbon atoms on the sheets are therefore accessible to Firstly, a thoughtful and necessary comparison among GR
protons that can readily transform to H2 by accepting photo- and its carbon allotropes e.g., CNT, C60 and activated carbon,
generated electrons from the carbon atoms. This work demon- which is often neglected in the literature, ought to be carried out
strates the potential of graphitic materials as a medium for water in order to better understand the essential advantages of GR and
splitting under solar illumination. 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
5. Future perspectives
time224–227 and recent years have seen a quite same phenomenon
In this updated review, the current status of applications of caused by the emergence of GR. Before the research interest in
graphene (GR)-based nanocomposites for photocatalytic synthesis of GR-based composite photocatalysts, a large body of
processes have been summarized, including nonselective research works regarding CNT-, C60- and activated carbon-
processes for degradation of pollutants, selective organic trans- based photocatalysts have also been reported in literature.146,228
formations for synthesis of fine chemicals and water splitting to In view of these facts, we wonder since the functions of carbon
clean hydrogen energy. It is clear that GR-based materials can materials lie in their chemical inertness, high adsorption capacity
serve as a new family of promising photocatalysts. The intro- and excellent charge mobilities,46 is GR different from other
duction of GR into various semiconductor photocatalysts as well carbon allotropes in essence and what is the substantial advan-
as metal nanoparticles can improve the photocatalytic perfor- tages of GR over its forbears? Our group15,78 has carried out
mance of semiconductors or metal nanoparticles owing to the some preliminary studies in this intriguing aspect. Taking CNT–
extended light absorption range, high adsorption capacity, P25 as an example and degradation of pollutants as model
specific surface area and superior electron conductivity of GR. reactions, we found that the key features for GR–P25, including
Undoubtedly, the promising opportunities offered by GR are enhancement of adsorptivity of pollutants, light absorption
outstanding. However, some existing challenges merit attention intensity, electron–hole pairs lifetime, extended light absorption
in order to achieve more efficient GR-based photocatalysts. In range and decreased photocatalytic activity with high content of
other words, some fundamental and essential issues are still GR, can also be observed in the composite of CNT–P25.15
unaddressed. For instance, as discussed in previous Considering the unique structural property of graphene oxide
reviews,12,16,45,46,48,223 the underlying mechanisms of GR-based (GO), the precursor of GR, we improved the synthesis approach
materials applied in energy related systems are not fully under- by using ‘‘soft’’ integration which leads to an intimate interfacial
stood and careful designs of the functional composites are contact between TiO2 and GR. In order to harness the electron
required to achieve more efficient performance. In fact, in conductivity of GR efficiently, one should utilize the superior
addition to these problems, there are other challenges in this and easily accessible ‘‘structure-directing’’ role of GO. Compared

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with the CNT–TiO2 counterpart, GR–TiO2 exhibits a much Fourthly, the approaches for producing GR need to be
more active visible light photocatalytic activity toward selective improved with more work on the preparation of GR or graphene
oxidation of alcohols to aldehydes. Our results indicate that oxide (GO) sheets with high quality, such as high purity, few
more efficient GR–semiconductor photocatalysts can be devel- defects, controlled size, lateral area and shape. So far, one of the
oped through rational design and engineering of the GR surface most commonly used methods to produce GR is the strong
with semiconductor ingredients. Our comparison study suggests oxidative exfoliation of graphite in a solution phase (GO is
that it is inevitable to draw a comparison amongst the carbon obtained by this step) followed by chemical reduction of GO.
materials (GR, CNT, C60 and activated carbon) to get answers to Although this approach is effective for mass production of GR, it
the above questions and, thus, enable GR to play its part better inevitably produces a large number of defects in the GR nano-
in improving the photocatalytic performance of semiconductors. sheets due to the change in its aromatic structure and the
More recently, Ye et al.175 have reported that the CdS–GR formation of oxygen-containing groups, which could diminish
nanocomposites with an optimized mass ratio exhibit higher the electrical conductivity and mechanical strength of GR,
photocatalytic activities than the CdS–CNT counterpart for both thereby deteriorating the photocatalytic performance of the GR-
the evolution of hydrogen and the degradation of methyl orange based nanocomposites. Although most of the functional groups
Published on 26 July 2012 on http://pubs.rsc.org | doi:10.1039/C2NR31480K

under visible light irradiation, which is ascribed to the stronger can be removed by the reduction procedure, only partial resto-
interaction or larger contact interface between CdS and GR. ration of the sp2-conjugated graphene network can be achieved.
However, there are still fundamental questions worthy of further Banhart et al.229 have reported that some of the predicted
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study. For example, if we prepare GR–semiconductor and CNT– extraordinary properties of GR can only be observed at an
semiconductor nanocomposites which both feature intimate extremely low defect concentration. The defects strongly affect
interfacial contact in a similar way, how different is their pho- the electronic, optical, thermal and mechanical properties of GR;
toactivity? Currently, our group is actively carrying out studies in besides, each defect has a certain mobility parallel to the GR
this regard. plane which weakens the ability of GR sheets in the transport of
Secondly and notably, one of the most common approaches electrons. The results obtained by Hersam’s group demonstrate
reported in the literature to prepare GR-based nanocomposites is the effects of defects on the photocatalytic performance of GR.169
based on the dispersion of semiconductor solid particles, which They found that the nanocomposites based on the less defective
refers to ‘‘hard’’ integration, on the surface of GR nanosheets. solvent-exfoliated graphene (SEG) exhibit significant enhanced
Such a strategy introduces GR merely for the sake of GR itself photocatalytic activity compared to that of solvent-reduced
without putting it into full play with elaborate design and is unable graphene oxide (SRGO), which is due to the superior electrical
to utilize the structural advantage of 2D GR.78 Consequently, a mobility of SEG. Thus far, studies on the production of high-
quite poor interfacial contact between the semiconductor and GR quality GR are scarce.169 Therefore, the production of large-scale
scaffold is often obtained. Since one of the key roles of GR in the GR sheets with minimal defects or oxidation sites, particularly
GR-based composite photocatalysts is to transfer the photo- with controlled size and shape, is still challenging and significant
generated electrons, an unsatisfactory interfacial contact is not for practical applications.
propitious for GR to play its role, and will weaken the synergetic Fifthly, it is necessary to clarify that a single GR nanosheet is
effect of GR and photoactive semiconductor and diminish the the standard form of GR and the superior properties of GR are
photocatalytic performance of the GR-based photocatalysts. associated with an individual sheet, such as the extremely large
Given this issue, the development of more efficient synthesis specific surface area and optical transparency. However, due to
methods or strategies is much more desirable to make full use of the strong cohesive van der Waals energy of the p-stacked layers
the structural and electronic merits of GR for achieving improved, in graphite and the high surface area of GR, the GR or GO tends
superior photocatalytic performance. to undergo irreversible agglomeration, being present in the multi-
Thirdly, as mentioned above, there is room to improve the layer form. Notably, when the layer number is fewer than 10, GR
interfacial contact between GR and semiconductor components properties vary as a function of layer number and interlayer
in GR-semiconductor photocatalysts in order to improve the ordering.4 For example, single-layer GR is a zero-gap semi-
overall photocatalytic performance. However, this significant conductor with a linear energy dispersion so that its charge
issue is not just a problem of tighter connection between each carriers can be viewed as massless particles that travel at an
respective component in GR-based composite photocatalysts, effective speed of 106 m s1. Bilayer GR is likewise a zero-gap
but also about optimization of the atomic charge transfer path semiconductor whose electrons obey a parabolic energy disper-
from the different respective components materials, which sion. A tunable bandgap of several hundred meV can be induced
probably needs to involve band bending calculations. In addi- in bilayer GR by breaking the symmetry between the two GR
tion, some interfacial mediators, possibly transition metal ions or layers by carefully applying a gate bias.230 As for trilayer GR, it is
metal nanoparticles, could help optimize the charge transfer in a semi-metal with a band overlap that can be controlled by an
the interface of GR-based composite photocatalysts. In this external electric field.231 Despite the recent burst of activity on the
regard, besides the experimental efforts, theoretical calculations production of GR, comparatively little progress has been made
on the interfacial band composition and regulation should be toward the generation of GR with tailored thickness, lateral area,
paid attention. A joint effort between experiment and theory size and shape.4 Therefore, in order to further improve and
would significantly advance our in-depth insight into the exploit the performance of GR and GR-based composite pho-
microscopic charge transfer pathway for GR-based photo- tocatalysts, the precise definition and synthesis of free-standing
catalysts, which in turn offers a guide towards the design target GR must be taken into account and paid sufficient attention.
of smarter GR-based photocatalysts for potential applications. Notably, the stacking of GR has been observed widely for

This journal is ª The Royal Society of Chemistry 2012 Nanoscale, 2012, 4, 5792–5813 | 5809
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The support by the National Natural Science Foundation of 31 F. Schedin, A. K. Geim, S. V. Morozov, E. W. Hill, P. Blake,
China (NSFC) (20903023, 21173045), the Award Program for M. I. Katsnelson and K. S. Novoselov, Nat. Mater., 2007, 6, 652–
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32 S. Watcharotone, D. A. Dikin, S. Stankovich, R. Piner, I. Jung,
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