Ultrasonics Sonochemistry 18 (2011) 1082–1090

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Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Sonochemical synthesis of TiO2 nanoparticles on graphene for use as photocatalyst

Jingjing Guo a, Shenmin Zhu a,⇑, Zhixin Chen b, Yao Li a, Ziyong Yu a, Qinglei Liu a, Jingbo Li a,
Chuanliang Feng a, Di Zhang a,⇑
a
State Key Laboratory of Metal Matrix Composites, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, PR China
b
Faculty of Engineering, University of Wollongong, Wollongong, NSW 2522, Australia

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

Article history: Using ultrasonication we succeed in a controlled incorporation of TiO2 nanoparticles on the graphene lay-
Received 29 November 2010 ers homogeneously in a few hours. The average size of the TiO2 nanoparticles was controlled at around
Received in revised form 14 March 2011 4–5 nm on the sheets without using any surfactant, which is attributed to the pyrolysis and condensation
Accepted 17 March 2011
of the dissolved TiCl4 into TiO2 by ultrasonic waves. The photocatalytic activity of the resultant graphene–
Available online 8 April 2011
TiO2 composites containing 25 wt.% TiO2 is better than that of commercial pure TiO2. This is partly due to
the extremely small size of the TiO2 nanoparticles and partly due to the graphene–TiO2 composite struc-
Keywords:
ture consisting of homogeneous dispersion of crystalline TiO2 nanoparticles on the graphene sheets. As
Graphene
Ultrasonication
the graphene in the composites has a very good contact with the TiO2 nanoparticles it enhances the
Photocatalysis photo-electron conversion of TiO2 by reducing the recombination of photo-generated electron–hole pairs.
Nanocomposite Ó 2011 Elsevier B.V. All rights reserved.

1. Introduction trochemical methods, chemical vapor deposition methods [8], ion-

Graphene (GR), a flat monolayer of carbon atoms tightly packed
into a two-dimensional honeycomb lattice. It has recently at-
tracted a great deal of attention for potential applications in many
fields, such as nanoelectronics, fuel-cell technology, supercapaci-
tors and catalysts [1–5]. Several approaches, including microme-
chanical exfoliation of graphite [6,7], chemical vapor deposition
[8,9], and solution-based chemical reduction [10–12] have been
developed to produce single-layered graphene. Unfortunately, the
yield of single-layer graphene sheets from various production
methods is quite low [10,12–16]. An even more serious problem
is that single-layer sheets of graphene are not stable in solution
and tend to aggregate back to graphite gradually because of the
strong Johannes Diderik van der Waals interactions [17].
One possible technique of preventing aggregation and harness-
ing the unique properties of single-layer graphene would be to
incorporate graphene sheets into composite materials. Many metal
or metal oxide nanoparticles, such as Au, Ag, Pt, Pd, TiO2, SnO2, and
MnO2 have been deposited on graphene sheets [18–22]. These me-
tal or metal oxide nanoparticles not only prevent the aggregation
of graphene sheets into graphite but also combine with the special
two-dimensional (2D) graphene, giving rise to some unique elec-
tronic, optical and catalytical properties which may be used in
applications, such as biologic sensing, photocatalysis, optoelec-
tronic and electrochemical devices [23]. Approaches, such as elec-
⇑ Corresponding authors. Tel.: +86 21 34202584; fax: +86 21 34202749.
E-mail addresses: smzhu@sjtu.edu.cn (S. Zhu), zhangdi@sjtu.edu.cn (D. Zhang).
exchange methods, intercalation [20], hydrothermal reduction
methods [24], sol–gel methods [25], and inner modification fol-
lowed by in situ reduction methods, have been developed to incor-
porate nanoparticles inside graphene sheets [21]. To be effective as
spacers, the nanoparticles have to adhere to the surface of the
graphene as uniformly as possible. Therefore, the control of the for-
mation and distribution of nanoparticles on the graphene layers is
critical.
Ultrasonication has proved to be an effective technique for gen-
erating nanoparticles with attractive properties in a short period of
reaction time [26–28]. The enhanced chemical effect of ultrasound
is due to acoustic cavitation phenomena: the rapid formation,
growth, and the collapse of bubbles in liquid. The extremely high
local temperature (>5000 K), pressure (>20 MPa) and very high
cooling rates (>1010 Ks 1) confer sonicated solutions unique prop-
erties, and are able to reduce metal ions to metal or metal oxide
nanoparticles [29,30]. The major advantage of this method, apart
from its fast quenching rate and operation at ambient conditions,
is that it is a simple and energy efficient process. In our previous
work [31], sonochemical method has been employed successfully
for the synthesis of TiO2 butterfly wings from butterfly templates.
TiO2 has attracted much attention on account of its high photo-
conversion efficiency [32]. TiO2 can produce photo-induced elec-
tron–hole pairs under the irradiation of ultraviolet (UV) light. From
the point view of photo-conversion efficiency, the photocatalytic
properties of TiO2 can be further enhanced if the recombination
of the photo-induced electron–hole pairs can be effectively
suppressed. Graphene–TiO2 composites are thus promising photo-
catalytic materials because graphene can act as an electron transfer

1350-4177/$ - see front matter Ó 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2011.03.021
 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090
channel thus reduces the recombination of the photo-generated
electron holes, and leads to improved photo-conversion efficiency
[33,34]. It was reported that a mixture of commercially pure TiO2
(P25) powder and graphene showed a relatively high photocata-
lytic property [24]. However, the particle size of P25 was relative
large and in micrometers and thus the photocatalytic property
can be further improved if the size of TiO2 is reduced to nanome-
ters. In fact, TiO2 particle size needs to be reduced down to
nanometers in order to improve the photocatalytic activity for
liquid-phase oxidation.
In this paper, we report a sonochemical method that embeds
TiO2 nanoparticles into graphene oxide (GO) nanosheets homoge-
neously without functionalizing the surface with a surfactant.
Graphene–TiO2 composite (GR–TiO2) was obtained by chemical
reduction of the graphene oxide–TiO2 composite (GO–TiO2). The
photocatalytic properties of the obtained GR–TiO2 composites
were investigated by measuring the photo-degradation of methy-
lene blue under UV-light, which demonstrated a high photocata-
lytic performance for the obtained composites.
2. Experimental
2.1. Preparation of GO
GO was prepared from natural graphite (crystalline, 300 mesh,
Alfa Aesar) by a modified Hummers method [35]. The detailed pro-
cessing is described as below: 2 g of graphite and 1 g of NaNO3
were mixed with 46 ml of H2SO4 (98%) in a 250 ml wide necked
bottle placed in an ice bath. Then, the mixture was stirred for
30 min. While maintaining magnetic vigorous stirring, a certain
amount of KMnO4 (6 g) was added to the suspension carefully.
After that, the ice bath was replaced by an oil bath, and the mixture
was stirred at 15 °C for 2 h. As the reaction progressed, the mixture
gradually became pasty, and the color turned into light brownish.
The next step was to increase the reaction temperature to 40 °C
and keep for another 1 h. Then, 92 ml of H2O was slowly added
to the pasty mixture with vigorous agitation. The reaction temper-
ature was rapidly increased to 98 °C with effervescence, and the
color changed to yellow. Finally, 30 ml of 5% H2O2 was added to
the mixture and allowing the high-temperature reaction to go on
for 1 h. For purification, the mixture was rinsed and centrifugated
with 5% HCl and deionized water for several times. After filtration
and drying under vacuum at 60 °C, GO was obtained as a gray
powder.
2.2. Preparation of GO–TiO2
GO–TiO2 composite was synthesized by sonochemical reaction
of TiCl4 in the presence of the GO. The detailed process is described
as follows: firstly, TiO2 precursors were prepared with the molar
ratios of ethanol: H2O: TiCl4 = 35:11:1, then, 0.25 g of the GO was
added and stirred for 0.5 h at ambient temperature, and finally
the suspension was sonicated at room temperature for 3 h using
a high-intensity ultrasonic probe (Ti horn, 20 kHz, 100 W/cm2).
The resulting composite was recovered by centrifugation and rins-
ing with ethanol solvent several times, then dried under vacuum at
60 °C. The obtained sample is called GO–TiO2.
2.3. Preparation of GR–TiO2
Chemical conversion of GO–TiO2 to GR–TiO2 was carried out by
using a reduction method [36]. In a typical reduction experiment,
0.7 g of GO–TiO2 powder was dispersed in 180 ml of deionized
water and the mixture was sonicated for 1 h. Next, 24 ml of hydra-
zine (85%) was added into the mixture under magnetic stirring and
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stirred for 24 h at 50 °C. GR–TiO2 composite was obtained by filtra-
tion and drying under vacuum at 60 °C. After calcination at 450 °C
for 3 h under nitrogen, crystallized GR–TiO2 composite (GR–TiO2–
T) was obtained.
2.4. Preparation of graphene
Graphene was obtained by chemical conversion of GO according
to the literature [36]. In a typical reduction experiment, 0.5 g of GO
powder was dispersed in 150 ml of deionized water and the mix-
ture was sonicated for 1 h. Next, 18 ml of hydrazine (85%) was
added under magnetic stirring, and the mixture was continuously
stirred at 50 °C for 24 h. Finally, black graphene powder was
obtained by filtration and drying under vacuum at 60 °C.
2.5. Characterization
The synthesized samples were characterized by X-ray diffrac-
tion (XRD) using a RigakuD/max2550VL/PC system operated at
40 kV and 40 mA with Cu Ka radiation (k = 1.5406 Å), at a scan rate
of 5° min 1 and a step size of 0.050° in 2h. Nitrogen adsorption
measurements at 77 K were performed using an ASAP2020 volu-
metric adsorption analyzer, after the samples had been outgassed
for 8 h in the degas port of the adsorption apparatus. Field-emis-
sion scanning electron microscopy (FE-SEM) was performed on a
JEOL JSM-6360LV field emission microscope at an accelerating
voltage of 15 kV. Transmission electron microscopy (TEM) and en-
ergy-dispersive X-ray measurements (EDX) were carried out on a
JEOL 2010 microscope at 200 kV. TEM specimens were prepared
by grinding the synthesized samples into powder with a mortar
and pestle and the powder was dispersed in pure ethanol and
picked up with holey carbon supporting films on copper grids. Fou-
rier transform-infrared measurements (FT-IR) were recorded on
KBr pellets with a PE Paragon 1000 spectrophotometer. Thermal
gravimetric analysis (TGA) was conducted on a PE TGA-7 instru-
ment with a heating rate of 20 °C/min. X-ray photoelectron spectra
(XPS) were collected on a physical electronics PHI5400 using Mg
Ka radiation as X-ray source. All the spectra were corrected with
the C1s (285.0 eV) band. Diffuse reflectance electronic spectra were
measured with a Perkin–Elmer 330 spectrophotometer equipped
with a 60 mm Hitachi integrating sphere accessory.
2.6. Photocatalytic experiments
30 mg of catalyst (GR, TiO2, and GR–TiO2–T) was dispersed in a
40 ml 0.02 g/L aqueous solution of methylene blue dye in a quartz
test cell. The reaction system was kept saturated with oxygen by
purging a slow stream of oxygen at ambient temperature. Before
irradiation, the reactor was stirred constantly in the presence of
oxygen in dark for 30 min, and then irradiated by four UV lamps
(6 W each) at room temperature. The photocatalytic activity was
evaluated on the basis of decrease of the absorbance band of the
methylene blue at 665 nm recorded at a regular time interval fol-
lowing the UV illumination. The absorbance measurement of the
reaction solution was taken after separating the TiO2 from the
reaction system by centrifugation.
3. Results and discussion
3.1. Characterizations
Wide-angle XRD patterns of the pure TiO2, GR, GR–TiO2 and
GR–TiO2–T are given in Fig. 1. The very broad peak at 2h = 25.5°
of GR–TiO2 indicates that TiO2 in the sample is largely of amor-
phous in nature. After the calcination at 450 °C, this peak at
1084 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090
Fig. 1. XRD of TiO2, GR, GR–TiO2 before and after calcinations under nitrogen.
2h = 25.5° becomes relatively narrower and resolved, indicating
that nanocrystalline TiO2 formed on the graphene. However, the
peak is still too broad to be used to estimate the size of crystallites
with Scherrer equation [37]. Nevertheless the broad peak suggests
that growth of the nanocrystalline TiO2 on the graphene was very
limited during the calcinations.
The loading of the TiO2 nanoparticles on the graphene was
determined by performing TGA in air by heating up from 40 to
900 °C (Fig. 2). A significant mass loss was observed at tempera-
tures from 510 to 700 °C for both GR and GR–TiO2–T, due to the
destruction of the carbon skeleton (carbonyl/double bond) of
graphene. The weight loss of GR–TiO2–T was stabilized at 75% at
temperatures between 700 and 900 °C, which indicates that the
amount of TiO2 loaded on the graphene sheets was about 25 wt.%.
Fig. 3 shows secondary electron images of GR before and after
the functionalization with TiO2 (GR–TiO2–T). The pure graphene
has a layered structure with a very smooth surface (Fig. 3a, c and
e). The GR–TiO2–T composite shows a mass of wrinkles both on
the edge of graphene sheets (Fig. 3b, d and f) and on the interlayer
sheets (see the circles in Fig. 3b, d and f). The layered structure of
Fig. 2. TGA curves of GR and GR–TiO2–T (heating rate = 20 °C/min under air
atmosphere).
the graphene sheets in the GR–TiO2–T composite exhibited nano-
scale textures, indicative of a much rougher surface (Fig. 3b). At a
high magnification (Fig. 3d), we can clearly see the uniform disper-
sion of TiO2 nanoparticles on both the graphene surface and the
interlayers. There is no agglomeration in the composite as shown
in the SEM image of the GR–TiO2 sheet (Fig. 3f). Fig. 3f also shows
that the TiO2 particle size was in nanometers which will be further
characterized by using TEM.
Fig. 4 shows TEM images of TiO2 loaded on the graphene layers
before (GR–TiO2) and after the calcination at 450 °C for 3 h (GR–
TiO2–T). For the as-synthesized GR–TiO2 (Fig. 4a), there are plenty
of wrinkles (in circles and at the edge) on the clean sheet owing to
the 2D nature of the sheet. The edges of the sheets are folded and
give the appearance of ribbons. High-magnification TEM micro-
graphs (Fig. 4b and c) reveal no discrete and well defined nanocrys-
talline TiO2 particles on the graphene sheets. However EDX (see
Supporting Information, Fig. s1) shows the presence of Ti, O and
C in the sample. The corresponding selected area electron diffrac-
tion pattern (SAED) of the composite shows that diffraction spots
of the graphite superimposed with the diffraction rings of TiO2
nanoparticles. After the calcination at 450 °C for 3 h, discrete and
well defined TiO2 fully crystallized particles were uniformly scat-
tered on the sheets as shown in Fig. 4d and the particle size is
around 4–5 nm from the high resolution image (Fig. 4f). This obser-
vation is consistent with the wide angle XRD results presented ear-
lier (Fig. 1). The inset in Fig. 4f is the SAED of GR–TiO2–T, and it can
be seen that the sample has a clear sixfold pattern of the graphene
and the diffraction rings of the TiO2 nanoparticles. The existence of
elements Ti, O and C was detected by EDX analysis (see Supporting
Information Fig. s2). As demonstrated in Fig. 4e, the measured lat-
tice-fringe spacing of 0.34 nm in the ribbons corresponds to the
(0 0 2) of the graphene sheets, where the crystal lattice of TiO2
nanoparticles is also resolved. From Fig. 4f the measured lattice
fringe spacing of 0.355 nm in GR–TiO2–T composites corresponds
to the (1 0 1) of anatase TiO2 (JCPDS 21-1272). No agglomeration
of the TiO2 particles was observed in this sample, which is usually
observed in samples prepared by other methods [20,24].
The TEM images shown in Fig. 4 confirm that a uniform disper-
sion of TiO2 nanoparticles on the graphene sheets have been
achieved under sonochemical reactions without the use of any sur-
factant. Which means ultrasound is very effective in dispersing
TiO2 nanoparticles on graphene layers.
In order to understand the texture of the composites, nitrogen
isothermal adsorption technique was employed to investigate the
ultrasonic irradiation effect on the pore structure as well as to
determine the location of the TiO2 in graphene (Fig. 5). The shape
of the isotherm for GR–TiO2–T was similar to that of the parent
GR, indicating the presence of open pores. It has a specific surface
area of 49 m2g 1 according to the BET (Brunauer, Emmett and Tell-
er) analysis. The P/P0 position of the inflection points is related to
the pore size in mesopore range, and the sharpness of these steps
indicates the uniformity [38]. As the relative pressure increases,
both the isotherms of GR and GR–TiO2–T exhibit sharp inflections
in the P/P0 in the range 0.5–0.6, a characteristic of capillary con-
densation within a uniform of interlayer spacing. Interestingly,
the space layer distribution of the starting GR centered at 2.6 nm
but disappeared when the TiO2 was loaded, suggesting the possi-
bility that titanium oxide formed first in this interlayer spacing.
As a result, the space layer distribution of GR–TiO2–T is more uni-
form than that of the pure GR from pore size distributions shown
in Fig. 5 (inset). The metal oxide nanoparticles increased the dis-
tance between the GR sheets to several nanometers, thereby mak-
ing the both faces of the graphene accessible.
The light-absorbance property of the samples was studied with
a UV–vis spectrophotometer and the measured UV–visible diffuse
reflectance electronic spectra are shown in Fig. 6. The absorption
 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090
Fig. 3. FE-SEM images of GR (a, c, e) and GR–TiO2–T (b, d, f) in different magnifications.
bands of GR–TiO2–T appeared to be fairly different from that of
P25. Because the appearance of TiO2 is white whereas the GR–
TiO2–T is black, the Kubelka–Munk theory could not apply to this
sample with such a strong adsorption. Therefore, the quantitative
consideration is void between TiO2 and GR–TiO2–T. However, a
broad and strong absorption in the visible light region was ob-
served for GR–TiO2–T due to the presence of 75 wt.% GR in the
GR–TiO2–T composite which acts as a ‘‘dyade’’ structure [39]. This
enhanced light-harvesting intensity of GR–TiO2–T could be possi-
bly explained by the formation of the chemical bonding between
TiO2 and GR, i.e. a Ti–O–C bond which favors charge transfer upon
light excitation [40].
The formation of the Ti–O–C bond was confirmed by FT-IR spec-
troscopy as shown in Fig. 7. GO depicts a strong OH peak at
3389.4 cm 1 and other C–O functionalities such as COOH
(1726.6 cm 1) and COC/COH (1383.3–1055.3 cm 1) are clearly vis-
ible. The spectrum also shows a C@C peak at 1617.5 cm 1 corre-
sponding to the remaining sp2 character. After the hydrazine
reduction, the characteristic absorption peaks (at 1726.6, 1383.3–
1055.3, and 591.2 cm 1) of GO disappeared due to the reduction
of oxygenous groups from the GO. As for GR–TiO2–T, the broad
absorptions at low frequencies (below 1000 cm 1) were ascribed
to the vibration of Ti–O–Ti bond (671.3, 683.9 cm 1) and Ti–O–C
bond (780.2 cm 1) which was not observed in the spectrum of
GR. This demonstrates that the TiO2 nanoparticles were strong
1085
chemically bonded on the graphene sheets, which was facilitated
by the sonochemical reaction. Further it was found that the peak
of the stretching vibration C-OH at 3419.7 cm 1 of GR shifted to
a higher wave number of 3443.8 cm 1 for GR–TiO2–T, which could
be explained by the influence of the formation of Ti–O–C bond.
Similar to that of GR, the skeletal vibration of the GR sheets at
1569.6 cm 1 was also clearly observed for GR–TiO2–T, illustrating
the formation of GR–TiO2–T composites. Due to the Ti–O–C bond
the TiO2 nanoparticles in GR–TiO2–T did not grow much upon cal-
cinations, i.e. the host graphene sheet prevented the nanocrystals
from sintering.
Complicated titanium coordination states in GR–TiO2–T, were
revealed from the XPS results. Fig. 8a shows the Ti 2p XPS spectra
of GR–TiO2–T, GR and GO. As expected, there are two peaks, Ti 2p3/2
centered at 458.5 eV and Ti 2p1/2 at 464.2 eV in the XPS spectrum
of GR–TiO2–T, which were not detected in the spectra of GR and
GO. Fig. 8b shows the XPS spectra of GR–TiO2–T, GO and GR in
the binding energy range between 280 and 294 eV (C 1s). The
two peaks at 287 and 285 eV of GO indicate a considerable degree
of oxidation of the graphite. The binding energy of 285 eV is due to
non-oxygenated ring C (284.3 eV), and 287 eV is due to the C in C–
O bonds (285.2 eV), the carbonyl C (C@O, 287.4 eV) and carboxyl C
(COOH, 289.1 eV) respectively [41]. Both the C 1s in the XPS spec-
tra of GR and GR–TiO2–T exhibit only a single strong peak at
284.3 eV which is attributed to elemental carbon, with a weak
1086 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090

Fig. 4. TEM images of GR–TiO2 before (a–c) and after calcinations (GR–TiO2–T) (d–f) in different resolutions.

Fig. 5. N2 adsorption/desorption isotherms of samples GR and GR–TiO2–T and the

corresponding pore size distributions (inset). Fig. 6. Diffuse reflectance electronic spectra of pure TiO2 and GR–TiO2–T.
 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090
Fig. 7. FT-IR spectra of GO, GR and GR–TiO2–T.
Fig. 8. (a) The Ti 2p XPS spectra of GO, GR and GR–TiO2–T, (b) the C 1s XPS spectra of GO, GR and GR–TiO2–T, (c) the survey XPS spectra of GO, GR and GR–TiO2–T.
1087
shoulder at 285.4 eV due to the oxygen functionalities (C–O
bonds), indicating considerable de-oxygenation by the reduction
process. There is an additional component at 286.4 eV correspond-
ing to the C in the C–N bonds of hydrazine, attributed to partial
reduction of carbonyl functionalities to hydrazone groups for GR
and GR–TiO2–T. The XPS survey scans of GR and GR–TiO2–T
(Fig. 8c) show that the characteristic peak at 400.98 eV (N 1p, cor-
responding to nitrate), which for GR–TiO2–T is considerably smal-
ler because some of N element was lost during the calcination. The
peak at around 281 eV, ascribed to Ti–C bonds was not detected in
GR–TiO2–T, suggesting that carbon was not doped into the lattice
of the TiO2.
3.2. Proposed mechanism
A uniform distribution of fine TiO2 particles on graphene sheets
has been achieved by a sonochemical method as described in Fig. 9.
Firstly, the process is involved in a simple physisorption of Ti
ion on graphene sheets. GO is known to consist of oxidized graph-
ene sheets that have their basal planes mostly decorated with
epoxide and hydroxyl groups, in addition to a few carboxyl groups.
Carboxylic moieties can interact with the metal cations through
1088 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090

Fig. 9. The proposed TiO2 nanoparticles formation mechanism on the graphene sheets by sonochemical method.

physisorption, electrostatic binding, or through charge-transfer

interaction. The Ti ions might become attached to the carboxyl
groups, and the reaction to TiO2 takes place on the surface of the
exfoliated sheets. However, the number of ionizable carboxyl
groups at the edge is not enough to complex the metal cations
and to stabilize the metal oxide particles formed, resulting in less
homogeneous and large particles. Generally, surface functionaliza-
tion is needed in order to be effective for homogeneous dispersion
[22]. A surfactant such as SB12 is generally used to control the size
of nanoparticles and to prevent aggregation [42]. Here in our pro-
cess, fine TiO2 nanoparticles were formed on the surface of graph-
ene without surface modification or additional agent. The unique
properties of ultrasonication may have effects on the formation
of nanoparticles.
Ultrasound agitation disperses solutes homogeneously in the
mixture and enhances the diffusion rate of TiCl4 to the surface of
GO, which can interact with the metal cations forming Ti–O–C
bonds on the GO surface as evidenced by FT-IR (Fig. 7). The chem-
ical effect of the ultrasound arises from acoustic cavitation, the for- Fig. 10. Photo-degradation of methylene blue solution under UV-light over GR, TiO2
mation, growth, and implosive collapse of bubbles in a liquid. The and GR–TiO2–T, respectively.

aggregation of the TiCl4 on the surface of the GO sheets can be sig-

nificantly retarded by the collapse of small bubbles, resulting in a
layer coating, a few nanometers thick, on the GO surface, which
is consistent with the disappearance of layer spacing at 2.6 nm
from the BET analysis. As a result, uniform dispersion of fine TiO2
forms in situ without any surface functionalization. The one-step
formation of the TiO2-graphene composites under ultrasonic irra-
diation illustrates the simplicity and efficiency of the sonochemical
approach as compared with the commonly used sol–gel’s proce-
dure which is generally complex and very time-consuming.
3.3. Photocatalytic measurements
The photocatalytic activities of GR–TiO2–T were measured by
the photo-degradation of methylene blue as model reaction under
UV-light (6400 nm), and the results are shown in Fig. 10. For a
comparison, the photocatalytic activities of commercial TiO2 and
pure GR were also measured under the same condition. In order
to exclude the influence of adsorption process, a time of 60 min
was allowed to achieve adsorption equilibrium before the photo-
catalytic reaction. Fig. 10 shows that the concentration of methy-
lene blue decreases fast with irradiation time both for TiO2 and
GR–TiO2–T, but almost no concentration change was observed for
the pure GR, illustrating that the photocatalytic reaction is related
to the existence of active sites (here TiO2). The pseudo-first-order
reaction was observed for the both TiO2 and GR–TiO2–T (Fig. 11).
For GR–TiO2–T, the k value at 0.0139 is higher than that of P25
at 0.0054; a high k value is well known to have a high photocata-
lytic activity. Photocatalytic efficiency can be affected by three
things: crystalline phase, surface area and hierarchical structures.
It is also well known that the activity is proportional to the surface
area accessible to the liquid. A large surface area could adsorb sig-
nificant amounts of water thus hydroxyl groups which can react
with photo excited holes and produce hydroxyl radicals which
are powerful oxidants in degrading organics. In this investigation,
the surface area of GR–TiO2–T was almost the same as that of
TiO2 but the former showed much higher photocatalytic activity
than the latter. This may be explained by the crystalline TiO2 nano-
particles prepared by sonochemical and calcinations approach,
which enhance the activity by facilitating the access to the reactive
sites of TiO2. Further, the graphene in the composite can act as an
electron transfer channel to reduce the recombination of the
photo-generated electron holes, and lead to improved photo-con-
version efficiency [33,34]. It should be noted that the weight ratio
of the TiO2 in GR–TiO2–T composite is only 25 wt.%, so the real
 J. Guo et al. / Ultrasonics Sonochemistry 18 (2011) 1082–1090
Fig. 11. Kinetic plots based on the data of Fig. 10.
photocatalytic activity of the TiO2 nanoparticles should be even
higher than commercial pure TiO2.
4. Conclusions
Using ultrasonication we succeed in controlled incorporation of
TiO2 on the graphene layers homogeneously in a few hours. The
average particle size of the TiO2 was controlled at around 4–
5 nm on the sheets without using any surfactant, which is attrib-
uted to the pyrolysis and condensation of the dissolved TiCl4 into
TiO2 by ultrasonic waves. The synthesis process is simple and effi-
cient. The photocatalytic performance of GR–TiO2–T containing
25 wt.% TiO2 is better than commercial pure TiO2. The much im-
proved photocatalytic activity of GR–TiO2–T, prepared by sono-
chemical method, is attributed to the graphene–TiO2 composite
structure consisting of very small and homogeneous dispersion
of crystal TiO2 on the graphene sheets. In this case the photocata-
lytic activity of the TiO2 is enhanced not only by the fine size
but also by the graphene which reduces the recombination of
photo-generated electron–hole pairs. Thus, such integration of
2D supports with large surface areas, and the highly dispersed
nanoparticles, can be an exciting material for use in future nano-
technology. These results and other related data demonstrate that
this sonochemical method may also be extended to synthesize
other metal oxides on graphene sheets, with high performance in
many potential applications, such as optical, electrical, catalysis,
sensors, and energy conversion devices and so on.
Acknowledgments
The authors gratefully acknowledge the financial support of this
research by the National Science Foundation of China (Nos.
51072117, 50772067), Shanghai Science and Technology Commit-
tee (Nos.06PJ14063, 07DJ14001), and Sino-French Project of MOST
of China (No. 2009DFA52410). We also thank SJTU Instrument
Analysis Center for the measurements.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.ultsonch.2011.03.021.
1089
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