pubs.acs.

org/JPCL

To What Extent Do Graphene Scaffolds Improve

the Photovoltaic and Photocatalytic Response of
TiO2 Nanostructured Films?
Yun Hau Ng,†,‡,§ Ian V. Lightcap,† Kevin Goodwin,† Michio Matsumura,‡ and
Prashant V. Kamat*,†
†
Radiation Laboratory and Department of Chemistry & Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556,
and ‡Research Center for Solar Energy Chemistry, Osaka University, 1-3 Machikaneyama, Toyonaka, 560-8531, Japan

ABSTRACT Graphene-TiO2 nanocomposites synthesized via a solution-based

method involving photocatalytic reduction of graphene oxide have been employed
as photoanodes. Nearly 90% enhancement in the photocurrent is seen as reduced
graphene oxide serves as electron collector and transporter. Additionally, the graphene-
TiO2 nanocomposite electrodes exhibit significant activity for the complete photo-
catalytic decomposition of 2,4-dichlorophenoxyacetic acid (2,4-D). Combined
with safe, solution-based synthetic practices, the promising photocurrent and
photocatalytic degradation rates provide the framework and motivation for the
implementation of graphene-TiO2 nanocomposites on larger scales.
SECTION Energy Conversion and Storage

Scheme 1. Electron Transport in Pristine TiO2 (left) and RGO-

C
arbon nanostructures such as fullerenes, carbon nano-
tubes, and graphene possess unique electronic and TiO2 Nanocomposite (right) Films Cast on an Optically Transpar-
ent Electrode (OTE)
catalytic properties.1-7 The recent emergence of stable
two-dimensional (2-D) carbon, graphene, has initiated a rapid
exploration of its potential in a broad range of fields such as
nanoelectronics, sensors, catalysis and nanocomposites.8-10
Owing to the existence of an extended sp2-bonded carbon
network, individual sheets of graphene possess excellent con-
ductivity. However, strong van der Waals interactions bet-
ween graphitic sheets make it difficult to isolate individual
graphene layers. Chemical functionalization or deposition of
metal nanoparticles keep sheets separate and further intro-
separated. Graphene sheet thicknesses obtained through
duce new electronic and optical properties for these carbon
this method typically correspond to mono- or bilayer gra-
nanostructures.9,11-14 Two common preparations for exfolia-
phene. Additionally, the process allows for control over the
ted graphene sheets are mechanical cleavage of highly pyro-
degree of reduction by adjusting exposure times. Solution-
lytic graphite15,16 and chemical treatment.11,17-19 Although
based graphene-TiO2 nanocomposites can thus be readily
mechanical cleavage of graphite has enabled the examination
formed in situ and are easily transferred or film-cast to a wide
of pristine graphene, its low yield significantly hinders it from
range of substrates.23 In recent years, several groups have
large-scale application. Chemical oxidation is a convenient,
employed such studies to explore photoelectrochemical and
scalable method that can be used to induce the exfoliation
photocatalytic properties of GO-TiO2 composites.24-28
of graphite into an aqueous dispersion of individual sheets of
The electron-accepting ability of carbon nanostructures
graphene oxide (GO). After oxidation, GO can be reduced
can be used to enhance electron transport properties of nano-
chemically to reduced graphene oxide (RGO) and partially
structured semiconductor electrodes (Scheme 1). By employing
restore the conductivity of pristine graphene while still main-
carbon nanotubes as scaffolding, we have shown the increa-
taining exfoliation. Although efficient, the chemical reduction
sed photocurrent generation efficiency in TiO2, CdS, and CdSe
by hydrazine can leave unwanted chemical residues and
nanostructured films.26,29-31 Employed as a scaffold, RGO
induce restacking of graphene sheets.18,20
can create a 2-D conductive support path for charge trans-
We have recently reported alternative reduction of GO
port and collection at the electrode surface. We present here
involving UV-assisted photocatalytic21 and sonolytic22 methods.
One advantage of photocatalytic reduction is the direct inter-
action between TiO2 nanoparticles and individual GO sheets. Received Date: May 28, 2010
Such an interaction facilitates delamination of RGO sheets Accepted Date: June 23, 2010
after reduction as the attached TiO2 particles keep them Published on Web Date: July 07, 2010

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the role of RGO in improving the photoelectrochemical and
photocatalytic performance of TiO2 nanostructured films.
Characterization of RGO-TiO2 Nanocomposites with Elec-
tron Microscopy. The morphology of RGO-TiO2 nanocompo-
sites was examined using a JEOL 2010 transmission electron
microscope (TEM) and a Hitachi S-4500 field emission scan-
ning electron microscope (SEM). Diluted samples of the
RGO-TiO2 nanocomposite were placed on Toray carbon
paper for SEM characterization. Images of the nanocomposite
reveal the entwined nature of graphene sheets in TiO2
nanoparticle networks.
Figure 1A shows an SEM image of the RGO-TiO2 nanocom-
posite with some graphene edges marked by dotted lines to
assist the reader. The SEM image in Figure 1B depicts a larger
graphene sheet emerging from the TiO2 assembly.
Transmission electron microscopy (TEM) was performed
in order to determine the nature of TiO2 adsorption on gra-
phene sheets. Diluted samples of RGO-TiO2 nanocomposites
were placed on holey carbon grids under N2 flow. The rela-
tively large holes in the TEM grid allow for unbound TiO2
nanoparticles to pass through, while large graphene sheets
with adsorbed TiO2 can be isolated. A TEM micrograph of a
graphene sheet obtained from the RGO-TiO2 nanocomposite
can be seen in Figure 2A. The selected area diffraction pattern
(SADP) exhibits reciprocal lattice spacings characteristic of
anatase TiO2 and graphene (inset). A high-resolution micro-
graph of individual TiO2 nanoparticles on graphene is shown
Figure 1. SEM images of RGO-TiO2 nanocomposites. (A) Typical
image of the nanocomposite to which dotted lines are added to
assist reader in distinguishing graphene sheet edges from TiO2
clusters. (B) Graphene sheet emerging from TiO2 clusters.
Figure 2. (A)TEM micrograph showing TiO2 nanoparticles adsorbed onto a graphene sheet. Inset shows the diffraction pattern taken from
sheet with spacings corresponding to graphene and anatase TiO2. (B) High-resolution image of TiO2 nanoparticles on graphene. Insets show
energy dispersive spectra (upper left) confirming the presence of TiO2 and magnification of the TiO2 lattice image (lower left).
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in Figure 2B along with elemental analysis verifying the pre-
sence of titanium.
Photoelectrochemical Behavior of Graphene-TiO2 Films.
Suspensions of known amounts of TiO2 and graphene were
deposited onto areas of ca. 2 cm2 of the optically transparent
electrode (OTE) by the drop cast method, as described pre-
viously.32,33 Careful deposition of the suspension results in the
formation of homogeneous RGO-TiO2 thin films as shown in
Figure 3. While a pure TiO2 thin film displays uniform white
color, the increasing addition of small amounts of graphene
gradually darkens the film color. The concentration of TiO2
was held constant at 2 mg/cm2, while the amount of graphene
was varied. We probed the photocurrent generation of the
RGO-TiO2 films by employing them as photoanodes in
photoelectrochemical cells. The photocurrent response of
RGO-TiO2 films at different graphene loadings is shown in
Figure 4A.
Upon irradiation with UV light, TiO2 particles undergo
charge separation to yield electrons (e) and holes (h). As the
holes are scavenged by OH- ions, the electrons are collected
by the OTE electrode to generate photocurrent. A photocur-
rent of ∼20 μA/cm2 was obtained using pristine TiO2 films.
The photocurrent response was prompt and reproducible
during repeated on/off cycles of illumination. At concentra-
tions below 0.05 mg/cm2 we see an increase in photocurrent
with increasing RGO content. A significant increase (∼90%)
in photocurrent generation up to ∼38 μA/cm2 was observed
with 0.05 mg/cm2 RGO RGO-TiO2 nanocomposite films. The
observed enhancement in the photocurrent represents impro-
ved charge transportation from the TiO2 through the RGO-
TiO2 nanocomposites to the collecting electrode surface. At
higher graphene loadings (>0.05 mg/cm2), light absorption by
RGO adversely affects the excitation of TiO2 nanoparticles. This
effect is also observed in the I-V curves of RGO-TiO2 nano-
composite films in Figure 4B, where cell performance begins to
decrease beyond an optimum graphene loading.
To further examine the photoelectrochemical properties of
the nanocomposites, the incident photon-to-photocurrent
efficiency (IPCE) of the films was examined. The RGO-TiO2
films reduced by photocatalytic and chemical reduction
(hydrazine) were compared with pristine TiO2 films. The IPCE
spectra were obtained using a monochromatic excitation
2223 DOI: 10.1021/jz100728z |J. Phys. Chem. Lett. 2010, 1, 2222–2227

source and calculated by normalizing the photocurrent to the
incident light energy and intensity using eq 1,
IPCEð%Þ ¼ 100 1240  I sc =ðP  λÞ ð1Þ
Where Isc is the short-circuit photocurrent (A/cm ), P is the
2 tion in drinking water. Advanced oxidation processes are
incident light intensity (W/cm2), and λ is the wavelength
(nm). All films (TiO2, RGO-TiO2 (in situ GO reduction), and
RGO-TiO2 (hydrazine GO reduction) exhibit similar photore-
sponse patterns in the UV region, obtaining a maximum IPCE
value at a wavelength of ∼350 nm, as shown in Figure 5. Films
composed of TiO2 without graphene yield a maximum IPCE
value of 7.4%. The RGO-TiO2 nanocomposite films yield
maximum IPCE values of 13.9% for the in situ RGO (photo-
catalytic reduction) and 11.4% for the hydrazine RGO (chemical
reduction using hydrazine). As shown earlier,32 the majority
(>90%) of the charge carriers generated following UV-
excitation of TiO2 undergo recombination. Quick capture
followed by transport of electrons is an important aspect in
enhancing the overall photoconversion efficiency. The high-
er IPCE values for the RGO-TiO2 films confirm graphene's
role as an electron collector, suppressing charge recombina-
tion in photoexcited TiO2.
Figure 3. Photographs of TiO2 thin films with different graphene
loadings.
Figure 4. (A) Photocurrent response versus time profiles and (B) I-V characteristics of OTE/graphene-TiO2 with different amounts of
graphene. Light is illuminated from the backside of the OTE.
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Photocatalytic Degradation of 2,4-Dichlorophenoxyacetic
Acid. One of the applications of such carbon-TiO2 composites
is in the remediation of contaminated water. Runoff from
fields is often a source of pesticide and herbicide contamina-
often useful in degrading herbicides such as 2,4 dichlorophe-
noxyacetic acid (2,4-D).34 Early studies have highlighted the
ability of RGO-TiO2 nanocomposites to act as efficient
photocatalysts27 and electrocatalysts.35-37
The merits of TiO2-assisted photocatalytic degradation of
2,4-D compared to other oxidation processes such as radioly-
sis and sonolysis has been discussed in detail previously.34,38,39
Upon excitation by UV light, electron-hole pairs are genera-
ted within TiO2. As the electrons are scavenged by dissolved
oxygen, the holes participate in the generation of OH 3
radicals that oxidize 2,4-D. The holes can either directly
oxidize the organic substrate or can transfer to the adsorbed
water to form hydroxyl radicals.
TiO2 þ hν f TiO2 ðe þ hÞ ð2Þ
TiO2 ðeÞ þ O2 þ graphene f TiO2 þ O2 - þ grapheneðeÞ
ð3Þ
TiO2 ðhÞ þ OH - f TiO2 þ • OH ð4Þ
TiO2 ðhÞ þ • OH þ 2; 4-D f degradation products ð5Þ
34,38,39
As confirmed in our previous mechanistic studies,
the herbicide is initially oxidized by hydroxyl radical to form
the intermediate 2,4-dichlorophenol (2,4-DCP). The oxidation
process further transforms the intermediates into quinones
and ultimately to carboxylic acids. Figure 6A shows UV-vis
absorption spectra recorded during the photocatalytic decom-
position of 2,4-D solution (aqueous, O2 saturated) at UV-
irradiated RGO-TiO2 film. The TiO2 and RGO-TiO2 films
were inserted in a photolysis cell and irradiated with UV-light
filtered through CuSO4 filter. Since the herbicide absorbs only
at wavelengths less than 300 nm (an intense and sharp peak
2224 DOI: 10.1021/jz100728z |J. Phys. Chem. Lett. 2010, 1, 2222–2227

at 230 nm and a broad peak at 285 nm), we can carry out selec-
tive excitation of TiO2 in the 300-350 nm region. Further-
more, the absorbance at 230 nm can be monitored to obtain
the concentration of remaining 2,4-D in solution. As we con-
tinue to irradiate the RGO-TiO2 film with UV light, we see a
decrease in the absorption bands of 2,4-D, indicating the
photocatalytic degradation of the herbicide in about 80 min.
Figure 6B shows the decrease in 2,4-D concentration with
irradiation time in the absence and presence of TiO2 and RGO-
TiO2 nanocomposite films. The blank experiment carried
out in the absence of the catalyst film confirms that photo-
lysis of 2,4-D under our experimental conditions has no noti-
ceable effect. On the other hand, both TiO2 and RGO-TiO2
are quite effective in degrading 2,4-D, but with a different
rate. The degradation half-lives observed for these two sets
of experiments were 147 and 38 min for pristine TiO2 and
RGO-TiO2 films, respectively. The decay of 2,4-D during the
initial period of UV excitation was fitted to pseudo-first-order
kinetics (inset Figure 6B). The rate constants for 2,4-D de-
gradation were 0.002 min-1 and 0.008 min-1 for TiO2 and
Figure 5. Photocurrent action spectra of TiO2-only film compa-
red with RGO-TiO2 nanocomposite films prepared by photocata-
lytic reduction and hydrazine reduction methods.
Figure 6. (A) Absorption spectra of aqueous solution (O2 saturated) of 0.15 mM 2,4-D recorded following UV-excitation of RGO-TiO2 film.
(B). The decrease in 2,4-D concentration following the UV photolysis with TiO2 and RGO-TiO2 films. The blank experiments recorded in the
absence of photocatalyst are also shown. Inset shows the pseudo-first-order fit of 2,4-D decay during initial 30 min of UV excitation.
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RGO-TiO2 films, respectively. The 4-fold increase in the rate of
photocatalytic degradation parallels the improvement in the
photoelectrochemical behavior of RGO-TiO2 films.
When we compare the improved photoelectrochemi-
cal and photocatalytic performance of the RGO-TiO2 films,
a 2-fold enhancement is observed in the photocurrent res-
ponse, while the increase in the photocatalytic degradation
rate is 4-fold. In addition to the improved charge separation,
the graphene sheets can overcome the mass transfer limita-
tion by increasing the availability of 2,4-D near the photo-
catalyst surface. Graphitic-based materials have already been
employed in the removal of organic pollutants.40 Earlier stu-
dies have shown that TiO2 deposited on adsorbent supports
such as activated carbon and silica can have significant influ-
ence in concentrating pollutant from low solution-phase con-
centrations.41,42 We expect a similar 2,4-D-rich environment
at the graphene/TiO2 interface to be an important contribut-
ing factor for achieving higher degradation rate.
The experimental results discussed here highlight the dual
role of graphene-based carbon nanostructures in improving
the photoelectrochemical and photocatalytic performance of
semiconductor nanoparticles. The improved photocurrent
generation is attributed to the ability of graphene sheets to
capture and transport charge to the collecting electrodes. The
faster rate of 2,4-D degradation observed with RGO-TiO2
points out the additional benefit of concentrating the organics
near the photocatalyst surface. Such beneficial aspects of
2-D nanostructures need to be further exploited to design
next-generation photocatalyst and solar cell devices. Indeed,
one such strategy of anchoring semiconductor and metal
nanoparticles on a single graphene sheet for designing a
2-D catalyst mat was demonstrated recently.28 Efforts are
underway to develop graphene-based catalysts with multi-
functional activities.
EXPERIMENTAL METHODS
Materials. Graphite powder (conducting grade, -325 mesh)
was purchased from Alfa Aesar; hydrazine hydrate and 2,4-D
2225 DOI: 10.1021/jz100728z |J. Phys. Chem. Lett. 2010, 1, 2222–2227

(98%) were purchased from Aldrich; P25 TiO2 nanoparti-
cles were obtained from Degussa. Other reagent-grade
chemicals were purchased from Fisher Scientific and used
as supplied.
GO was synthesized using a modified Hummers
method.43 The GO powder obtained was filtered and washed
with 1 M HCl and deionized water. A 5.0 mg/mL TiO2
suspension was prepared by the addition of Degussa P25
TiO2 powder to methanol under stirring. Dispersions of GO
in methanol were added to TiO2 suspensions and sonicated
for 30 min to produce GO-TiO2 dispersions. Dispersions
were then purged with N2 and exposed to UV-irradiation
through an aqueous CuSO4 filter (>320 nm) for 30 min using
an Oriel 450 W xenon arc lamp to obtain RGO-TiO2
composites. Typical concentrations for TiO2 and GO were
1 mg/mL and 0.5 mg/mL, respectively. The ratio of GO to
TiO2 was varied to investigate the photoelectrochemical
properties of the RGO-TiO2 nanocomposite. The obtained
nanocomposites were deposited onto OTEs by dropwise
addition under flowing air. Films were calcined at 673 K
in air for 1 h and are referred to as RGO-TiO2 films. For
comparison, RGO-TiO2 films were made using hydrazi-
ne-RGO. This involved the addition of 1 M hydrazine
hydrate solution to the GO dispersion followed by a treat-
ment at 80 °C for 6 h.
Photoelectrochemical Measurements. Thin films of RGO-
TiO2 nanocomposite material were cast and employed as
electrodes in photoelectrochemical and photocatalytic cells to
determine the benefit of composite material versus TiO2
alone. Half cell reactions were conducted using Pt foil as the
counter electrode and 1 M KOH as the electrolyte. An Oriel
450 W Xe lamp with a CuSO4 filter was employed as the light
source. The intensity of the incident light near the electrode
surface was 100 mW/cm2. The photoelectrochemical proper-
ties were measured with a Keithley model 617 electrometer.
The incident photon to charge carrier generation efficiency
(IPCE) was recorded using a Princeton Applied Research
model PARSTAT 2263 potentiostat.
Photocatalytic Degradation of 2,4-D. Photocatalytic decom-
position of 2,4-D involved the addition of 3 mL of 0.15 mM
2,4-D into a cuvette containing an RGO-TiO2 film. An Oriel
Apex Illuminator with a glass filter that removed light with
wavelengths lower than 320 nm was used as the light source.
The system was purged with O2 gas throughout the experi-
ment. The thin film sample was immersed in the 2,4-D
solution in dark conditions for 30 min prior to the irradiation
to allow the equilibration between analyte and catalyst parti-
cles. Degradation of 2,4-D was monitored using a Cary 50 Bio
UV-vis spectrophotometer.
SUPPORTING INFORMATION AVAILABLE Absorption spec-
tra of RGO. This material is available free of charge via the Internet at
http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author:
*To whom correspondence should be addressed. E-mail: pkamat@
nd.edu.
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Present Addresses:
§
Current address: ARC Centre of Excellence for Functional Nano-
materials, School of Chemical Engineering, The University of
New South Wales, Sydney NSW 2052, Australia.
ACKNOWLEDGMENT Y.H.N. thanks the Global Center of Excel-
lence (GCOE) of Osaka University for the summer fellowship to
conduct research at Notre Dame. K.G. thanks the NDNano Center
for awarding a NURF summer fellowship. The research described
herein was supported by the Department of Energy, Office of Basic
Energy Sciences. This is contribution number NDRL 4856 from the
Notre Dame Radiation Laboratory.
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