Journal of Colloid and Interface Science 377 (2012) 114–121

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

ZnO/graphene-oxide nanocomposite with remarkably enhanced

visible-light-driven photocatalytic performance
Benxia Li ⇑, Tongxuan Liu, Yanfen Wang, Zhoufeng Wang
School of Materials Science and Engineering, Anhui University of Science and Technology, Huainan, Anhui 232001, People’s Republic of China

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

Article history: In this work, a high-performance photocatalyst of ZnO/graphene-oxide (ZnO/GO) nanocomposite was
Received 30 December 2011 synthesized via a facile chemical deposition route and used for the photodegradation of organic dye from
Accepted 20 March 2012 water under visible light. The nanocomposite was characterized by X-ray diffraction, X-ray photoelectron
Available online 28 March 2012
spectroscopy, scanning electron microscopy, transmission electron microscopy, Brunauer–Emmett–
Teller N2 adsorption–desorption analysis, and UV–Vis diffusion reflectance spectroscopy. The ZnO/GO
Keywords: nanocomposite consisting of flower-like ZnO nanoparticles anchored on graphene-oxide sheets has a
ZnO
high surface area and hierarchical porosity, which is benefit to the adsorption and mass transfer of dye
Graphene oxide
Nanocomposite
and oxygen species. For the photodegradation of organic dyes under visible light, ZnO/GO nanocomposite
Synthesis exhibited remarkably enhanced photocatalytic efficiency than graphene-oxide sheets and flower-like
Photocatalysis ZnO particles. Moreover, the photocatalytic efficiency of ZnO/GO nanocomposite could be further
Visible light improved by annealing the product in N2 atmosphere. The outstanding photocatalytic performance
was ascribed to the efficient photosensitized electron injection and repressed charge carriers recombina-
tion in the composite with GO as electron collector and transporter, thus leading to continuous genera-
tion of reactive oxygen species for the degradation of methylene blue.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction
Currently, organic dyes and their effluents have become one of
the main sources of water pollution due to the greater demand in
industry such as textile, paper, and plastic. These organic dyes con-
taminate environment by the release of the toxic, cancerogenic,
and colored wastewater [1–5]. Most of these dyes escape from tra-
ditional wastewater treatment and persist in water because of
their high stability against light, temperature, chemicals, and
microbial attack [3–5], whereas photocatalytic degradation of the
organic pollutants has opened a new door for the elimination of
organic dyes in wastewater [6–10]. The photodegradation process
utilizes cheaply available semiconductors and leads to complete
mineralization of organic compounds to CO2, water, and mineral
acids [11]. Thus, semiconductor photocatalysis is deemed to an
alternative technique to remove various organic pollutants. Until
now, ZnO and TiO2 photocatalysts have been widely used because
of its strong oxidizing power, non-toxic nature, and low cost [12–
16]. ZnO is a wide band-gap semiconductor oxide (3.37 eV) with a
conduction band edge located at approximately the same level as
that of TiO2. More attractively, the electron mobility of ZnO has
been proven to be higher than that of TiO2 [17]. However, despite
⇑ Corresponding author. Fax: +86 554 6668643.
E-mail address: libx@mail.ustc.edu.cn (B. Li).
its great potential, the photocatalytic efficiency remains very low
because of the fast recombination of the photogenerated elec-
tron–hole pairs in the single phase semiconductor.
The performance of semiconductor photocatalysts is often en-
hanced by means of noble metal loading [18–20], ion doping
[21,22], and incorporation of electron-accepting materials [23–
25]. These actions are used to extend the light absorption range
or suppress the electron–hole recombination. As a rising star of
carbon family, graphene has become the focus of considerable
interest because of its unique electronic properties and other
excellent attributes, such as the large theoretical specific surface
area and the high transparency [26–29]. Meanwhile, graphene
oxide (GO) is receiving increasing attention because it possesses
the similar properties to graphene as well as the special surface
structures with the introduced hydroxyl and carboxyl groups for
synthesis of GO-containing nanocomposites [30–38]. Particularly,
the fabrication of semiconductor/GO composites has attracted sub-
stantial research efforts motivated by the desire to improve the
photocatalytic efficiency [34–38]. The recent studies have revealed
that the composites simultaneously covered three excellent attri-
butes: the increasing adsorptivity of pollutants, extended light
absorption range, and efficient charge transportation and separa-
tion [25,39], which are the ideal traits of a photocatalyst we have
been pursuing for. Therefore, it is believed that anchoring well-
organized ZnO nanostructures on GO sheets can efficiently utilize

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.03.060
 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121
the combinative merits of ZnO and GO to obtain a photocatalyst
with superior performance.
This work demonstrated a facile strategy to synthesize ZnO/GO
nanocomposite consisting of flower-like ZnO nanoparticles an-
chored on GO sheets and its use for photocatalytic degradation of
organic dye in water under visible light. The composition, mor-
phology, and microstructure of the as-obtained ZnO/GO nanocom-
posite were characterized. The photocatalytic performance of ZnO/
GO nanocomposite was evaluated by the photodegradation of
methylene blue in water and compared with that of pure flower-
like ZnO nanoparticles and GO sheets, to highlight the importance
of the anchoring of ZnO nanoparticles on GO sheets for maximum
utilization of ZnO photocatalyst and GO as electron collector and
transporter in photocatalytic degradation of organic pollutants.
2. Experimental
2.1. Materials
Graphite flakes (200 mesh) were purchased from Qingdao
Tianyuan Company. 37% hydrochloric acid (HCl), 98% sulfuric acid
(H2SO4), 85% phosphoric acid (H3PO4), 30% hydrogen peroxide
(H2O2), potassium permanganate (KMnO4), zinc chloride (ZnCl2),
sodium hydroxide (NaOH), and absolute ethanol were purchased
from Shanghai Sinopharm Chemical Reagent Co. Ltd. All chemicals
were analytical grade without further purification. Deionized
water was used throughout this study.
2.2. Preparation of graphene oxide (GO) sheets
The graphene oxide was synthesized by chemical oxidation and
exfoliation of graphite flakes using an improved Hummers’ method
[40]. Graphite flakes (1.5 g) and KMnO4 (9.0 g) were successively
added into a 9:1 mixture of concentrated H2SO4/H3PO4
(180:20 mL) under continuous stirring. The reaction was heated
at 50 °C and stirred for 12 h. Then, the reaction was cooled to room
temperature and poured onto ice (200 mL) with 30% H2O2 (3 mL).
The mixture was then repeatedly centrifuged and washed in suc-
cession with water, 30% HCl solution, and ethanol. The obtained so-
lid product of GO was finally dried at 80 °C.
2.3. Preparation of ZnO/GO nanocomposite
To synthesize ZnO/GO composite, 0.1 g dried GO precipitate
was dispersed in 40 mL of water to form GO suspension by ultra-
sonication, in which a further exfoliation of GO was achieved. Then,
zinc chloride (ZnCl2, 1.0 mmol, 0.1364 g) and sodium hydroxide
(NaOH, 10.0 mmol, 0.4000 g) were successively dissolved in the
above GO suspension. The mixture was sealed in a glass bottle
(60 mL), kept static at 90 °C for 6 h, and then cooled to room tem-
perature naturally. Finally, the composite was filtered, washed sev-
eral times with distilled water and ethanol, and dried at 80 °C for
24 h. For comparison, flower-like ZnO nanoparticles were synthe-
sized by a similar method without adding GO. In addition, the
ZnO/GO product prepared via aqueous-solution route at 90 °C
was further annealed at 400 °C and in N2 for 2 h.
2.4. Characterizations of the samples
The products were characterized by X-ray diffraction (XRD, Shi-
madzu XRD-6000, Cu Ka radiation), field-emission scanning elec-
tron microscopy (FE-SEM, Sirion200), and transmission electron
microscopy/high resolution transmission electron microscopy
(TEM/HRTEM, H-7650 and JEOL-2010). X-ray photoelectron spec-
troscopy (XPS) measurements were performed on a VGESCALAB
115
MKII X-ray photoelectron spectrometer with an exciting source
of Mg Ka. The nitrogen adsorption and desorption isotherms at
77 K were measured using a Micromeritics ASAP 2000 system after
the sample was degassed in a vacuum at 130 °C overnight. The UV–
Vis diffuse reflectance spectra (DRS) were recorded on a recording
spectrophotometer of Perkin Elmer Lambda 950.
2.5. Photocatalytic property test
The photocatalytic properties of the samples were evaluated by
photodegradation of methylene blue (MB) in water under visible-
light irradiation from a 300 W Xe light equipped with a 420 nm
cutoff filter (CEL-HXF300/CEL-HXUV300, China). In every experi-
ment, 80 mg of photocatalyst was suspended in 100 mL of a
5.0  105 M aqueous solution of MB. Prior to irradiation, the sus-
pension was stirred in the dark for 2 h to achieve an adsorption–
desorption equilibrium between the photocatalyst and MB mole-
cules. After that, the solution was exposed to the visible-light irra-
diation under magnetic stirring. At given time intervals, 3 mL of
solutions was sampled for analysis of the MB concentration. The
photocatalytic degradation process was monitored using a UV–
Vis spectrophotometer (Shimadzu UV2550) to record the charac-
teristic absorption at 665 nm.
3. Results and discussion
3.1. The formation mechanism of ZnO/GO composite
In this work, ZnO/GO nanocomposite was fabricated by a two-
step aqueous-solution route. GO sheets were firstly prepared using
an improved Hummers’ method, and ZnO nanoparticles were then
anchored on GO sheets via a facile reaction between Zn2+ and OH
ions in aqueous solution. Fig.1 illustrates the fabrication process
and formation mechanism of ZnO/GO composite. It has been
proved that the surfaces of the chemically exfoliated GO sheets
are covered by a large number of hydroxyl, carboxyl, and epoxy
groups that are introduced on GO sheets due to oxidation proce-
dures [41,42]. These functional groups can act as anchor sites to
enable the subsequent in situ formation of ZnO nanoparticles on
GO sheets. The formation of ZnO/GO composite undergoes the fol-
lowing two distinctive stages: (i) when dissolving ZnCl2 into GO
suspension, Zn2+ ions will be adsorbed onto the surfaces of GO
sheets due to their bonding with the O atoms of the negatively
charged oxygen-containing functional groups via electrostatic
force. (ii) After the addition of NaOH, the crystal growth units of
ZnðOHÞ24 and ZnO
2
may combine with the functional groups of
GO sheets via intermolecular hydrogen bonds or coordination
bonds, acting as anchor sites for ZnO nanoparticles. With heating
at 90 °C, a large number of ZnO nuclei are formed in a short time
due to the hydrolysis reaction of ZnðOHÞ24 . Finally, ZnO/GO nano-
composite is obtained. The in situ formation of ZnO nanoparticles
in return caused the exfoliation of the lamellar GO.
3.2. XRD and XPS analysis
Fig. 2 shows the XRD patterns of ZnO nanoparticles, ZnO/GO
nanocomposite, and GO sheets, respectively. All the diffraction
peaks in the XRD pattern of ZnO nanoparticles are consistent with
the hexagonal phase wurtzite ZnO (JCPDS No. 36-1451). The dif-
fraction peak at around 2h = 8° in the XRD pattern of GO sheets be-
longs to the (0 0 1) reflection of GO, and the interlayer spacing
(0.95 nm) is much larger than that of graphite (about 0.37 nm) ow-
ing to the introduction of oxygen-containing functional groups on
the graphite sheet surfaces [43,44]. The diffraction peaks of ZnO/
GO nanocomposite are similar to those of hexagonal (wurtzite)
116 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121

Fig. 1. Illustration of the fabrication process and formation mechanism for ZnO/GO nanocomposite. (1) Oxidation of graphite to graphite oxide with larger interlayer spacing.
(2) GO sheets from the ultrasonic exfoliation of graphite oxide. (3) Adsorption and bonding of Zn2+ ions onto the GO sheets. (3) The nucleation and growth of ZnO crystallites,
resulting in ZnO/GO nanocomposite.

Fig. 2. (a) XRD patterns of ZnO nanoparticles, ZnO/GO nanocomposite and GO; (b–d) XPS spectra of ZnO/GO nanocomposite.

ZnO. Nevertheless, the (0 0 1) diffraction peak at 8° of GO dropped
profoundly to an almost undetectable level, which may indicate
that the regular layered structure of GO has been destroyed and
exfoliated GO sheets are formed due to the growth of ZnO nano-
crystals [31]. The XRD patterns demonstrate that the ZnO/GO
nanocomposite can be obtained in the present system. Further evi-
dence for the composition of the ZnO/GO nanocomposite was ob-
tained by the X-ray photoelectron spectra (XPS, Fig. 2b–d). The
survey spectrum (Fig. 2b) shows the presence of Zn and O as well
as C. The higher-resolution spectrum of Zn2p3/2 in Fig. 2c shows
that the level of Zn2p3/2 is 1021.68 eV. The C1s XPS spectrum of
ZnO/GO (Fig. 2d) clearly indicates a considerable degree of graph-
ene oxide with three main components that correspond to carbon
atoms in different functional groups: the non-oxygenated CAC
bond (284.79 eV), the CAO of epoxy and hydroxyl (286.15 eV),
and the carbonyl C@O (288.35 eV) [35–37]. The small peak at
 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121
290.71 eV can be ascribed to the p–p satellite of the aromatic con-
jugated domains modified with carboxylic acid, hydroxyl, and
epoxide groups in graphene oxide [45,46]. Therefore, the peak at
290.71 eV suggests the existence of a partially modified p structure
in the ZnO/GO nanocomposite.
3.3. SEM and TEM images
FESEM images in Fig. 3a–d show the morphologies and micro-
structures of GO sheets, pure ZnO nanoparticles, and ZnO/GO
nanocomposite, respectively. From the FESEM image in Fig. 3a,
the layered structure of the stacked GO sheets can be seen, and
there are many wrinkles through all the surfaces of GO sheets.
The solid GO sample is severely agglomerated because of its high
specific surface area. Fig. 3b shows an FESEM image of pure ZnO
nanoparticles, and it reveals that the detailed morphology of ZnO
is flower-like aggregates with diameters about 1 lm, assembled
by many densely arranged nanosheets. In the presence of GO mate-
rial, ZnO/GO nanocomposite with flower-on-sheet morphology
(Fig. 3c and d) was obtained under similar experimental condition
for preparing flower-like ZnO nanoparticles. As shown in Fig. 3c,
GO nanosheets were well decorated by the flower-like ZnO parti-
cles. Moreover, some ZnO particles entered into the interlayers of
GO sheets to form a sandwich-like composite structure (Fig. 3d),
which can prevent the stacking of GO sheets, and thus avoid the
loss of their high active surface area.
Fig. 4 shows TEM images of GO sheets and ZnO/GO composite. It
is observed from Fig. 4a that the GO sheets present a crumpled sur-
face, which is consistent with the observation from FESEM image.
Fig. 4b and c show TEM images with different sizes of ZnO/GO
nanocomposite. The light-gray thin films are the GO sheets, and
the dark regions on the GO background are due to the presence
of ZnO particles. It can be clearly seen in Fig. 4b that the exfoliated
GO sheet was decorated with ZnO aggregates with sizes of 0.5–
1 lm, whereas some of the flower-like ZnO microstructures on
GO sheets were crushed into fragments because of the ultrasonic
treatment before TEM observation. Moreover, the loaded
Fig. 3. FESEM images of (a) GO sheets, (b) pure ZnO, (c and d) ZnO/GO nanocomposite.
117
flower-like ZnO particles were mainly located at the edge of the
GO sheets, which might result from the aggregation of ZnO parti-
cles that confined their efficient dispersion on GO sheets. Fig. 4d
shows HRTEM image of a ZnO fragment marked with the circle
in Fig. 4c, which exhibits well-resolved two-dimensional lattice
fringes with the spacings of 0.52 nm and 0.28 nm, in good agree-
ment with the interplanar spacings of {0 0 0 1} and {0 1 1 0} planes
of hexagonal (wurtzite) ZnO.
3.4. N2 adsorption/desorption measurement
Due to the high surface area of graphene sheets (calculated va-
lue: 2630 m2 g1), a higher surface area of ZnO/GO nanocomposite
than pure ZnO is expected. The N2 adsorption–desorption iso-
therms at 77 K and pore-size distribution plot calculated by the
Barrett–Joyner–Halenda (BJH) method of ZnO/GO nanocomposite
are shown in Fig. 5. The isotherms (Fig. 5a) present a reverse ‘‘S’’
shape, which is identified as type IV and characteristic of mesopor-
ous structures [47,48] From the adsorption branch of the iso-
therms, the specific surface area of 234.0561 m2 g1 is calculated
for ZnO/GO nanocomposite through a multi-point Brunauer–Em-
mett–Teller (BET) method [49]. The distributions of pore sizes
shown in Fig. 5b indicate that there are two types of pores in the
ZnO/GO nanocomposite. One type of them is concentrated in the
range of typical mesoporous structure of 2.8 nm, which is probably
attributed to the interspaces between the layers of GO sheets. The
other type of pores with larger sizes distributes around 65.8 nm,
which presumably arises from the spaces between nanosheets in
the flower-like ZnO particles [12]. The average pore diameter of
16.6949 nm is calculated for ZnO/GO nanocomposite using a Bar-
ret–Joyner–Halenda (BJH) model. The cumulative volume of pores
with diameters between 1.7 and 300 nm is 0.9743 cm3 g1. For
comparison, the BET surface area of pure ZnO with flower-like
morphology was calculated to be 25.1617 m2 g1. The higher spe-
cific surface area and hierarchical porosity of ZnO/GO nanocom-
posite provide the possibility for the efficient adsorption and
mass transfer of the degradable organic molecules and hydroxyl
118 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121

Fig. 4. TEM images of (a) GO sheets, (b and c) ZnO/GO nanocomposite, (d) HRTEM image of a ZnO fragment marked with the circle in (c).

Fig. 5. (a) N2 adsorption–desorption isotherms at 77 K and (b) pore diameter distribution of ZnO/GO nanocomposite.

radicals in photochemical reaction, and a superior photocatalytic

performance of ZnO/GO nanocomposite should be expected.

3.5. UV–Vis diffuse reflectance spectra and photocatalytic performance

Fig. 6 shows UV–Vis diffuse reflectance spectra of pure ZnO and

ZnO/GO nanocomposite. ZnO sample shows the characteristic
spectrum with its fundamental absorption edge rising at 400 nm,
while the ZnO/GO composite shows absorption in the whole visible
region. Because ZnO and GO in the ZnO/GO composite are different
two phases, their band-gap energies were not changed [50]. The
absorption edge of ZnO can also be detected in the UV–Vis spec-
trum of ZnO/GO sample. Besides, an intense and broad background
absorption in visible region was observed due to the presence of
GO.
The photocatalytic performance of ZnO/GO nanocomposite was
evaluated by examining the photodegradation of methylene blue
(MB) as a representative pollutant under visible-light irradiation
from a 300 W Xe lamp. Prior to irradiation, the photocatalytic Fig. 6. UV–Vis diffuse reflection spectra of pure ZnO and ZnO/GO nanocomposite.
 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121 119

Fig. 7. (a) The time-dependent absorption spectra of MB solution (5.0  105 mol/L, 100 mL) in the presence of ZnO/GO nanocomposite (80 mg) and under visible-light
irradiation, and the inset is the color-change sequence of MB solution during this process. (b) Photodegradation of MB over photocatalyst-free solution (blank), GO sheets,
flower-like ZnO particles, ZnO/GO nanocomposite, and annealed ZnO/GO, respectively.

Fig. 8. (a) Kinetic linear simulation curves and (b) the reaction rates of photocatalytic degradation of MB over photocatalyst-free solution (blank), GO sheets, flower-like ZnO
particles, ZnO/GO nanocomposite, and annealed ZnO/GO, respectively.

reaction system was magnetically stirred in the dark for 2 h to photocatalytic efficiency, and 98.1% of MB was photodegraded
reach the adsorption/desorption equilibrium of MB on the surface from the aqueous solution after visible-light irradiation for
of the photocatalyst. Fig. 7a shows the UV–Vis absorption spec- 60 min. Moreover, the photocatalytic efficiency of ZnO/GO nano-
trum of the aqueous solution of MB (initial concentration, composite could be further improved by annealing the product in
5.0  105 mol/L; 100 mL) with 80 mg of ZnO/GO nanocomposite N2 atmosphere. The time-dependent absorption spectra of MB
obtained at low temperature as photocatalyst and exposure to solution in the presence of annealed ZnO/GO (80 mg) and under
the visible light for various durations. The characteristic absorption visible-light irradiation are shown in Fig. S1 (Supporting informa-
of MB at 665 nm decreases rapidly with extension of the exposure tion), which demonstrates that the characteristic absorption of
time, and almost disappears after about 60 min. Further exposure
leads to no absorption peak in the whole spectrum. The color-
change sequence in the MB solution during this process is shown
in the inset of Fig. 7a, from which it is clear that the intense blue
color of the initial solution gradually disappears with increasingly
longer exposure times. To demonstrate the synergy-induced
enhancement of the photocatalytic efficiency of ZnO/GO nanocom-
posite, contrastive experiments were performed using flower-like
ZnO particles and GO sheets as photocatalyst for the photodegra-
dation of MB, respectively. The results of the MB degradation in a
series of experimental conditions are summarized in Fig. 7b, where
C0 and Ct are the initial concentration after the equilibrium adsorp-
tion and the residual concentration of MB, respectively. Without
any photocatalyst (blank), there was hardly any degradation of
MB solution under visible-light irradiation. In the presence of GO
sheets, MB solution was just slightly degraded after 100 min. By
comparison, the degradation rate of MB in the presence of flow-
er-like ZnO particles is 54.3% after 100 min of irradiation. However,
Fig. 9. Cycling runs in the photocatalytic degradation of MB in the presence of ZnO/
ZnO/GO nanocomposite was found to exhibit very prominent GO nanocomposite (80 mg) and under visible-light irradiation.
120 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121
Fig. 10. Possible mechanism of photosensitized degradation of dye over ZnO/GO nanocomposite under visible light.
MB almost disappears after 40 min of the exposure time. As shown
in Fig. 7b, 97.9% of MB was photodegraded from the aqueous solu-
tion in the presence of the annealed ZnO/GO after only 40 min of
visible-light irradiation. The kinetic linear simulation curves of
photocatalytic degradation of MB with photocatalyst-free solution
(blank), GO sheets, flower-like ZnO particles, ZnO/GO nanocom-
posite, and annealed ZnO/GO are presented in Fig. 8a, respectively.
It is clear that the curve with irradiation time as abscissa and ln(Ct/
C0) as the vertical ordinate is close to a linear curve. The values of k
(Fig. 8b) for photocatalyst-free solution (blank), GO sheets, flower-
like ZnO particles, ZnO/GO nanocomposite, and annealed ZnO/GO
are 0.00072, 0.0024, 0.0077, 0.064, and 0.099 min1, respectively,
indicating that the ZnO/GO nanocomposite has remarkably en-
hanced photocatalytic activity, which may be attributed to the
interactions between the GO sheets and ZnO nanoparticles. Never-
theless, the photocatalytic activity of the ZnO/GO nanocomposite
obtained via aqueous-solution route at low temperature has not
achieved the best result because the surface of the product was
presented by a number of OH groups, which is believed to quench
photogenerated chargers. After annealed at 400 °C and in N2, the
OH groups were eliminated. Therefore, the annealed ZnO/GO
exhibited further improved photocatalytic efficiency. To demon-
strate the photocatalytic effect of ZnO/GO nanocomposite toward
a more stable dye, the photodegradation of methyl orange (MO)
in water under the visible-light irradiation was carried out. The
time-dependent absorption spectra of MO solution in the presence
of ZnO/GO nanocomposite (Fig. S2, Supporting information) indi-
cate that the characteristic absorption of MO almost disappeared
after about 80 min, and the color of MO solution changed gradually
from yellow to colorless after irradiation for 80 min.
The stability of photocatalyst during photocatalytic reaction is a
crucial factor for the practical applications. To test the reusability
of ZnO/GO nanocomposite in MB photodegradation, five cycles of
the photocatalytic experiment for ZnO/GO nanocomposite were
carried out. As shown in Fig. 9, MB could be totally decomposed
in each cycle and the ZnO/GO photocatalyst exhibited almost no
change in its photocatalytic activity during the repeated photocat-
alytic experiments. Thus, the higher photocatalytic activity and
reusability of ZnO/GO nanocomposite were beneficial for its appli-
cation as a photocatalyst.
The photocatalytic degradation of organic dyes by semiconduc-
tor under visible-light irradiation generally involves two mecha-
nisms. The first is based on the excitation of the semiconductor,
which involves excitation of the semiconductor by light irradiation
to form photogenerated electrons in the conduction band and
holes in the valence band, and the subsequent chemical reactions
with the surrounding media after the photogenerated charges
move to the particle surface [51]. The other mechanism is based
on the excitation of dye [52–54], in which the dye acts as a sensi-
tizer of visible light as well as injects excited electrons to an elec-
tron acceptor to become a cationic dye radical (dye+), followed by
self-degradation or degradation by the reactive oxidation species.
Such a photocatalytic degradation process for dyes has been dem-
onstrated to be an efficient approach to remove textile dyestuff
from aquatic environments [37,38,55,56]. Considering the wide
band-gap (3.37 eV) of ZnO, degradation of MB or MO under visible
light in the present case should be conducted following the dye-
excitation mechanism, as illustrated in Fig. 10. GO sheets with
large specific surface area and numerous oxygenic groups allow
good access of dye molecules to their surfaces in photocatalytic
system. For example, MB was firstly excited to MB, followed by
electron transfer to the conduction band of ZnO via the transporta-
tion in GO sheets, then the photoelectrons were captured by sur-
face-adsorbed O2 to generate the reactive oxidation species (such
as  OH;O2 ). Finally, the MB
+
radical was degraded itself or by
the formed reactive oxidation species. Such an efficient electron-
transfer process with GO as electron collector and transporter is
responsible for the enhanced photocatalytic performance under
visible light. As for GO sheets used as photocatalyst, although the
efficient electron-transfer process can be occurred between MB
and GO, a very slow reaction rate is caused by the electron accu-
mulation on GO surface and the rapid electron-MB+ recombina-
tion [56].
4. Conclusion
In conclusion, the ZnO/GO nanocomposite was successfully syn-
thesized via a facile chemical deposition route at low temperature
and its use for the photodegradation of organic dye from water un-
der visible light was investigated. The ZnO/GO nanocomposite is
composed of flower-like ZnO nanoparticles anchored on graph-
ene-oxide sheets. For the photodegradation of organic dyes from
water under visible light, ZnO/GO nanocomposite exhibits much
higher photocatalytic efficiency than GO sheets and flower-like
ZnO particles. The enhanced photocatalytic performance of ZnO/
GO nanocomposite can be attributed to the efficient photosensi-
tized electron injection and repressed electron recombination
due to the electron-transfer process with GO as electron collector
and transporter. These features make the ZnO/GO composite an
excellent candidate for applications relating to a number of envi-
ronmental issues. The preparation method may be extended to fab-
ricate more graphene-based composites for a variety of
applications, such as catalysts, gas sensors, and nanoelectronic
devices.
Acknowledgments
Financial supports from the National Natural Science Founda-
tion of China (21001003), Natural Science Foundation of Anhui
Province of China (10040606Q15), Natural Science Research for
Colleges, and Universities of Anhui Province of China (KJ2010
A101) are acknowledged.
 B. Li et al. / Journal of Colloid and Interface Science 377 (2012) 114–121
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2012.03.060.
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