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Chemical free synthesis of graphene oxide in the preparation of reduced

graphene oxide-zinc oxide nanocomposite with improved photocatalytic
properties

Article  in  Applied Surface Science · April 2018

DOI: 10.1016/j.apsusc.2018.04.138

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 Applied Surface Science 451 (2018) 67–75

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Full Length Article

Chemical free synthesis of graphene oxide in the preparation of reduced

graphene oxide-zinc oxide nanocomposite with improved photocatalytic
properties
Sunil Meti a, Mohammad R. Rahman a, Md. Imteyaz Ahmad b, K. Udaya Bhat a,⇑
a
Department of Metallurgical and Materials Engineering, National Institute of Technology Karnataka, Surathkal 575025, India
b
Department of Ceramic Engineering, Indian Institute of Technology (BHU) Varanasi, 221005, India

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

Article history: In the present investigation, the reduced graphene oxide – zinc oxide (rGO-ZnO) was prepared by rapid
Received 28 December 2017 microwave-assisted hydrothermal technique. The chemical free graphene oxide (GO), synthesized by
Revised 9 April 2018 Tang Lau technique, was used in the preparation of rGO-ZnO nanocomposite. The GO gets reduced to
Accepted 13 April 2018
rGO during microwave irradiation and provides the necessary nucleation site for the ZnO nanorods to
Available online 17 April 2018
grow in [0 0 0 1] direction. These ZnO nanorods were completely wrapped with rGO sheets, confirmed
by the synchrotron XRD and TEM techniques. The phases and cell parameters were calculated by
Keywords:
Rietveld method. The prepared composite was used for the photodegradation of methyl orange (MO)
Tang-Lau method
rGO-ZnO
dye from water under UV light. Investigation revealed that the incorporation of rGO into the ZnO
Microwave method increased the photodegradation ability of the bare ZnO. The performance of the composite is also com-
Structural properties pared with the rGO-ZnO nanocomposite, where rGO was prepared by Hummer’s method. rGO obtained
Photocatalysis from Tang Lau method formed stable and efficient composite with ZnO and exhibited higher activity
compared to the composite, wherein rGO was prepared from conventional Hummer’s method. Under
UV light, the ZnO liberates photoelectrons which reacts with surface oxygen to form superoxide radicals
(O


2 ) and (OH ) in the water medium. The rGO nanosheets could reduce the charge recombination during
the reaction. The active species adsorbs the MO molecules and degrades into CO2, H2O and other byprod-
ucts. More than 3.5 times increase in the rate constant was observed for rGO-ZnO compared to the bare ZnO.
Ó 2018 Elsevier B.V. All rights reserved.

1. Introduction instrumentation or usage of extremely strong chemical agents.

The small lateral sizes of synthesized product remained the major
Graphene is a two-dimensional single-atomic-thick sheet of drawbacks of these techniques [3]. Moreover, most of the
graphite, which possesses extraordinary physical, chemical and processing methods involve multiple steps where in controlling
mechanical properties [1]. The oxidized form of graphene, gra- the layer growth is difficult [17,23]. Recently, Tang et al. [3]
phene oxide, has attracted attention towards research in various reported a facile and low cost method for synthesis of GO utilizing
aspects of material science with a wide variety of possible applica- glucose, fructose and sugar as major ingredients. By employing
tions [2]. The GO has found many applications in the functional hydrothermal processing, GO was synthesized at much lower
devices, such as, fuel cells, supercapacitors, battery material, temperatures while, at the same time, by varying processing
nanofluids, photovoltaics, etc. [3–13]. Several synthesis methods parameters such as temperature, sugar concentration and duration
for GO has been reported. Most notable methods are chemical of heating, the number of layer could be controlled [3]. The
vapour deposition (CVD) [14], mechanical exfoliation method synthesis of GO by Tang Lau method is not explored much in the
[15], SiC pyrolysis [16], e-beam evaporation [17], Modified context of preparation of the nanocomposite.
Hummer’s method [18] and so on. By far, Hummer’s method has The ZnO is one of the highly attractive wide band gap semicon-
been most widely used technique for the synthesis of GO/rGO ductor material (3.37 eV, which is similar to that of GaN) with a
[19–22]. However, these techniques require either high end large binding energy (60 meV), at room temperature [13]. ZnO
has found applications in light emitting diode, varistors, transpar-
ent electrodes, pH sensors, biosensors, acoustic wave devices, UV-
⇑ Corresponding author. photodiodes, photocatalyst, laser diodes, gas sensors, etc. [24–29].
E-mail address: [email protected] (K.U. Bhat).

https://doi.org/10.1016/j.apsusc.2018.04.138
0169-4332/Ó 2018 Elsevier B.V. All rights reserved.
68 S. Meti et al. / Applied Surface Science 451 (2018) 67–75

Recently, there have been attempts of growing nanocomposite of make-Rigaku) using copper target (Cu Kɑ = 1.54 Å). Rietveld refine-
ZnO nanostructure with carbonaceous species to improve the ment of the obtained XRD pattern of rGO-ZnO nanocomposite was
properties of the bare ZnO [28–37]. The rGO content in the rGO- carried out using General Structural Analysis System (GSAS) soft-
ZnO nanocomposite assist charge transfer between the metal oxide ware suite [39,40]. The Bragg peak profiles were modeled with
and pollutants, thereby improving optoelectronic property, energy pseudo-Voight type-3 function. The quality of the GO was exam-
storage property and photocatalytic ability [38]. ined using Fourier transform infrared (FTIR, make-JASCO-4200)
In the present work, the initial GO with large lateral dimension spectrometer in ATR mode (attenuated total internal reflection)
was synthesized by Tang Lau method. The hydrothermally synthe- and Raman spectroscopy with 325 nm and 514 nm laser
sized GO was successfully reduced and anchored with ZnO nanor- (make-Horiba Jobin Yvon-LabRAM HR, Kyoto, Japan) radiation.
ods using microwave irradiation. The addition of rGO to ZnO Further, to identify the presence of rGO in rGO-ZnO nanocompos-
resulted in remarkable improvement in the photocatalytic activity ite, XRD patterns were also recorded at Stanford Synchrotron
when compared to that of the bare ZnO. The effect of rGO content Radiation Light-source (SSRL), Menlo Park, U.S.A. [41]. The
on photocatalytic performance of rGO-ZnO nanocomposite was diffraction pattern was recorded at incident X-ray energy of 12
demonstrated by monitoring the degradation of methyl orange keV, while x was fixed at 3°. In order to improve powder
(MO) dye. averaging, sample was rocked 1° during recording. The graph of
the diffracted intensity against the scattering vector ‘‘Q” was
plotted. The relation between scattering vector and ‘‘d” spacing
2. Experimental section
can be given by the equation:
2.1. Materials
2p
Q¼ ð1Þ
d
All chemicals used in the study were analytical-grade reagents
and used in as received condition without any further purification.
Combining the Eq. (1) with Bragg’s law, the scattering vector
Zinc nitrate hexahydrate (Zn(NO3)26H2O), sodium hydroxide
can be rewritten as:
(NaOH) and sucrose (C12H22O11) were purchased from Sigma-
Aldrich Chemicals, Mumbai, India. The deionised (DI) water was 4pSinðhÞ
used throughout the experiments. Q¼ ð2Þ
k

2.2. Synthesis of GO, rGO-ZnO and ZnO The X-ray photoelectron spectroscopy (XPS-Kratos Analytical,
UK, monochromatic Al Ka as X-ray source) was performed for
The GO was synthesized by a hydrothermal route (Tang Lau the surface analysis of the sample. All the XPS data was
method). 100 ml sugar solution (0.5 M) was prepared by dissolving calibrated by to the standard C1s peak of the surface adsorbed
sucrose in DI water. A Teflon lined stainless steel autoclave (capac- carbon at 284.7 eV. C 1 s, Zn 2p and O 1s peaks were recorded
ity 200 ml) was filled with the prepared sugar solution up to half at area resolution of 1 eV. The surface features and morphologies
the capacity. The autoclave was heated in hot air oven to a temper- of the synthesized materials were investigated by using field
ature of 180 ± 2 °C for 80 min. The autoclave was then cooled to emission scanning electron microscopy (FESEM, make-JEOL-
room temperature. GO was scooped from the solution and washed JSM-6380LA, Tokyo, Japan) and transmission electron microscopy
with DI water to remove the residues. (JEOL-JEM-2100, Tokyo Japan) while chemical analysis was
The rGO-ZnO nanocomposite was synthesized using microwave carried out using energy dispersive X-ray spectroscopy (Oxford
assisted hydrothermal method. 140 mg of GO was added to 20 ml Instruments, Oxfordshire, UK). Micro-Raman measurements
DI water and ultrasonicated for 30 min. 1.785 g (0.3 M) of Zn (make-Horiba Jobin Yvon-LabRAM HR, Kyoto, Japan) were
(NO3)2  6 H2O was added to the above solution. The whole solution carried out to characterize the structure of rGO in rGO-ZnO
was kept under constant stirring and 2 M NaOH solution in DI and the bare ZnO.
water was added drop-wise to achieve the pH of 10–11. The pre-
pared solution was transferred to a 24 ml capacity Parr acid diges- 2.4. Photo catalytic activity
tion vessel. The digestion vessel was heated in a microwave oven
(radiation frequency 2.45 GHz and power 700 W) in convection The photocatalytic ability of the prepared rGO-ZnO nanocom-
mode, for 10 min. After the microwave heating, it was found that posite and ZnO nanopowders were evaluated by monitoring the
the colour of the suspension had changed into grayish-black, indi- degradation of MO dye (25 mg/L) in aqueous solution. A 15 W
cating the successful chemical reduction of GO nanosheets (GONs) deuterium lamp was used as the UV light source. 50 ml each
[21]. The solution was transferred to a beaker and washed with DI of the above prepared MO dye solution was taken in two
water and ethanol for several times and finally the sample was separate beakers where, 25 mg of catalyst (rGO-ZnO and ZnO)
dried at 70 °C for 12 h. For comparison, bare ZnO nanoparticles was added separately. Initially the solution was kept in dark
were synthesized by following the same procedure as above with- and stirred for 30 min to establish absorption-desorption equi-
out adding GONs. librium between the dyes and photocatalysts. The solution
In order to look at the effect of Zn-precursor, the rGO-ZnO was then placed under the UV light and it was continuously
nanocomposite was synthesized using ZnCl2 as precursor for Zn stirred during the exposure. 5 ml solution from the system
in place of Zn(NO3)2  6 H2O, keeping all other processing parame- was collected at every 20 min time interval. The collected
ters same. The rGO-ZnO nanocomposite was also prepared from solution was centrifuged for few minutes to separate out the
GO synthesized using Hummer’s method to compare the catalytic catalyst in the solution. The absorbance intensity was measured
performance with that of GO prepared using Tang Lau method. at the wavelength of 464 nm using UV–visible double beam
spectrophotometer (Systronics, Model-2201, NITK Surathkal,
2.3. Characterization India). The relative degradation activity was expressed by
(Cf/Co) vs t, where Cf represents the real-time concentration of
Phase identification of the sample was carried out by using MO and Co represents the initial concentration after the
X-ray diffractometry (XRD, make-JEOL-JPZ 8 and thin film XRD, absorption-desorption equilibrium.
 S. Meti et al. / Applied Surface Science 451 (2018) 67–75 69

3. Results and discussion motion of symmetric CAC band, whereas, the D band is the result
of disruption in symmetric hexagonal graphitic lattice [45,46]. The
3.1. Characterization of GO synthesized by following hydrothermal intensity ratio (ID/IG) is a measure of disorder degree and average
method size of the sp2 domains in graphite materials [29]. The ID/IG peak
intensity is observed to be 0.873, which is attributed to the
Fig. 1a shows the XRD pattern of GONs synthesized using decrease in the size of in-plane sp2 domains and formation of
sucrose as the reagent in hot air hydrothermal autoclave. The defects and disorders in the GONs, as well as an increase in the
diffraction peak position for (0 0 2) reflection was observed at 2h edge planes [46]. The SEM micrograph of the GONs is shown in
9.5° indicating a d-spacing of 9.304 Å, which is greater than the Fig. 1d. From the micrograph it is confirmed that the hydrother-
d-spacing of 8.01 Å reported in the literature [42]. This increase mally synthesized GONs are made up of large continuous films.
in the d-spacing is attributed to the incorporation of carboxyl,
hydroxyl and epoxide groups in graphene sheets during hydrother- 3.2. Characterization of the rGO-ZnO nanocomposite synthesized by
mal synthesis [43]. using microwave assisted hydrothermal irradiation
FTIR spectrum of GONs is shown in Fig. 1b. The sharp peak at
2925 cm
1 is attributed to the stretching vibration of the CAH The XRD pattern of the rGO-ZnO nanocomposite and ZnO at
bond. The broad absorption peak centered at 3418 cm
1 indicates room temperature has been shown in Fig. 2a. The diffraction pat-
the hydroxyl (AOH) groups present in the GONs. The spectrum tern consists of highly intense well resolved peaks. The peaks exhi-
showed some narrow peaks in the range 3900–3600 cm
1. This is bit Bragg angle positions for P63mc space group in wurtzite
due to (cOH) mode of different types of the isolated hydroxyl symmetry [47,48]. All the peaks of ZnO were matching with the
groups [44]. The absorption peaks at 1022, 1393, 1700, 1613 JCPDS card no 36-1451 [28]. The 2h values for three major peaks
cm
1 correspond to alkoxy CAOAC, O@CAO, carbonyl C@O and of the ZnO nanopowder are at 31.7°, 34.45° and 36.2° which are
aromatic C@C stretching vibration modes, respectively [23]. These attributed to (1 0 0), (0 0 2) and (1 0 1) planes, respectively, while
results show that GONs have only C, H and O elements. C@C and minor peaks at 47.5°, 56.6°, 62.8°, 66.7°, 68.1° and 69.2°, corre-
CAC form a honeycomb framework with O and H decorating the spond to (1 0 2), (1 1 0), (1 0 3), (2 0 0), (1 1 2) and (201) planes,
GONs in the form of AOH, CAH, CAOAC and AC@O groups [3]. respectively. The observed diffraction peaks provide a clear evi-
Fig. 1c shows the Raman spectrum of GONs, where the charac- dence for the formation of a single phase wurtzite structure for
teristic D band and G band were observed at 1385 cm
1 and 1603 the ZnO. The peak intensities for rGO-ZnO nanocomposite is low-
cm
1, respectively. The G band corresponds to the in-plane stretching ered compared to the ZnO intensities due the interaction of rGO

Fig. 1. (a) XRD pattern, (b) FTIR spectrum, (c) Raman spectrum and (d) SEM images of the hydrothermally synthesized GONs.
70 S. Meti et al. / Applied Surface Science 451 (2018) 67–75

Fig. 2. (a) rGO-ZnO nanocomposite and ZnO XRD pattern, (b) Synchrotron XRD pattern, (c) Rietveld refined pattern of rGO-ZnO nanocomposite and (d) magnified image of the
synchrotron XRD pattern showing the presence of the carbon species, graphene (<10%), in the rGO-ZnO nanocomposite.

with ZnO. The XRD pattern of rGO-ZnO shown in Fig. 2a has been respectively [30]. These results indicate the chemical state of zinc
analyzed employing Rietveld refinement technique with the help as Zn+2 (+2 oxidation state). The O 1s peak is centered at 531.5 eV
of GSAS software suite. and C 1s peak at 285.75 eV (Fig. 3a). From Fig. 3c, the peak corre-
The Rietveld refined data for the XRD pattern is shown in Fig. 2c. sponding to O 1s was relatively wider and can be deconvoluted
The Fig. 2c shows the experimental, calculated and residual XRD into three peaks centered around 531.05, 532.25 and 533.35 eV
profiles for the rGO-ZnO nanocomposite. The low value of v2 indicating three kinds of oxygen-containing species. The O 1s
(goodness of fit) equal to 1.110 and Rwp of 11.9 % was achieved, peaks centered at 532.25 eV and 531.05 eV were attributed to
which may be considered to be good for estimations. The lattice the oxygen from absorbed water and ZnO, while the O 1s peak cen-
parameters calculated from refined data are a = b = 3.250814 Å tered around 533.35 eV was attributed to oxygen attached to the
and c = 5.207126 Å. These values are in good agreement with those rGO as CAO bond [49]. No peaks corresponding to C@O bonds were
reported in literature [48]. No XRD peak corresponding to rGO or observed, which, may be due to much lower content of C@O com-
any other carbon bearing species was observed. This is attributed pared to CAO in rGO-ZnO nanocomposite. The C 1s peak centered
to lower abundance of rGO in rGO-ZnO nanocomposite than detec- at 285.75 eV could also be deconvoluted into two peaks centered
tion limit of XRD. The XRD studies were further conducted using around 285.6 eV and 288.2 eV. The peak centered around 285.6
synchrotron radiation light source (Fig. 2b and d). The intense eV was attributed to CAC bond while the peak centered around
and relatively broad XRD peaks corresponding to ZnO was 288.2 eV was due to the presence of CAO/C@O bond [50]. The
observed indicating nanocrystalline nature of ZnO in the nanocom- CAC band is intense and sharp where as the CAO band is broad-
posite. Crystallite size of ZnO was estimated to be 31 nm using ened due to the loss of oxygen during reduction of GO into rGO.
Scherrer formula. A diffused hump close to the Q value 1.17 Å
1 Raman spectra for the rGO-ZnO and the ZnO are as shown in
(corresponding to the d-spacing of 5.37 Å) was also observed Fig. 4. The characteristic D and G bands for rGO were observed in
(depicted in Fig. 2d), which was attributed to the presence of the nanocomposite at 1386 cm
1 and 1604 cm
1, respectively.
rGO. The reduction in the d-spacing from 9.304 Å to 5.37 Å was However, the ratio ID/IG of rGO present in rGO-ZnO nanocomposite
attributed to the loss of oxygen which tends to move the was 0.91, which was greater compared to 0.873 (from GO, Fig. 1c),
d-spacing closer to the graphitic structure (3.35 Å). confirms the reduction of GO to rGO during microwave heating.
Fig. 3a shows the wide survey XPS spectrum of rGO-ZnO com- This increase in the intensity ratios is due to the decrease in the
posite powder. The spectrum reveals the presence of three ele- size of sp2 domains upon reduction and interaction between ZnO
ments, namely, carbon, oxygen and zinc. The XPS data matched and graphene sheets. The Raman shift for ZnO is observed at 437
well with the already reported data by Akhavan [29]. In Fig. 3b, cm
1, corresponding to E2 high frequency mode of wurtzite struc-
two peaks corresponding to Zn 2p core-level was observed at ture from C6v symmetry group [51,52]. The intensity of E2 high fre-
1022.5 and 1045.7 eV attributed to Zn 2P3/2 and Zn 2P1/2, quency mode of the bare ZnO is somewhat lowered by the
 S. Meti et al. / Applied Surface Science 451 (2018) 67–75 71

Fig. 3. (a) X-ray photoelectron survey spectrum, (b) Zn 2P peak, (c) O 1s peak and (d) C 1s peak of rGO-ZnO nanocomposite.

peaks corresponding to ZnO in rGO-ZnO nanocomposite are broad-

ened due to higher scattering and interaction of rGO with ZnO.
FESEM showed the detailed morphology of the rGO-ZnO
nanocomposite. It is observed that the ZnO nanorods are sand-
wiched between the rGO nanosheets as shown in Fig. 5a. The diam-
eter of the ZnO rods varied in tens of nanometers where as the
length in few hundreds of nanometers. To complement the results
of XRD and FESEM, the microstructure is further investigated by
using TEM. Fig. 5b and c show the TEM micrographs. It shows that
the rGO nanosheets are successfully stacked on to the ZnO nano
rods. The selected area electron diffraction (SAED) patterns from
the ZnO nanorods showed the intense diffraction spots indicating
that the ZnO nanorods were very well-crystallized. One of such
SAED patterns are depicted in the inset of Fig. 5c, from the region
marked as ‘‘P” in the micrograph. TEM-EDS in Fig. 5d spectrum
shows that C, O and Zn are the only elements present in the
nanocomposite.
Fig. 4. Raman spectra of the ZnO and the rGO-ZnO nanocomposite.
3.3. Growth mechanism of the ZnO and rGO-ZnO nanorods during
microwave heating
interaction of the rGO with the ZnO. Group theory predicts that the
A1, E1 and E2 optical modes are present at the point of Brillion zone. The ZnO crystals are obtained by microwave heating of the Zn
A1 and E1 symmetry are polar and get split into longitudinal optical (NO3)2 in strong alkaline solution using NaOH at 700 W power
(LO) and transverse optical (TO) phonons, all being Raman and for 10 min. Zinc dissociates into Zn2+ ions and the NaOH added
infrared active, and hence exhibit different frequencies [53,54]. to the solution dissociates into sodium ions (Na+) and hydroxyl
The structural defects in ZnO are represented by the peak at 582 ions (OH
) [55]. Amount of polar molecules and the hydroxyl ions
cm
1 which is assigned to E1 (LO) mode. The peak centered around concentration in the solution are increased. The chemical reaction
380 cm
1 and a small shoulder peak at 410 cm
1 are due to A1 (TO) is predicted as follows:
mode and E1 (TO) mode frequencies, respectively [51]. The peaks
centered around 330 cm
1 and 1145 cm
1 in ZnO sample are due ZnðNO3 Þ2 $ Zn2þ þ 2 NO
3
to multiple-phonon scattering process; whereas the intensity of
these peaks in rGO-ZnO nanocomposite is lowered. The Raman NaOH $ Na þ þOH

72 S. Meti et al. / Applied Surface Science 451 (2018) 67–75

Fig. 5. (a) and (b) show FESEM and TEM micrographs of the microwave assisted hydrothermally synthesized rGO-ZnO nanocomposite showing ZnO nano rods decorated with
rGO, (c) TEM micrograph with selected area electron diffraction (SAED) pattern and (d) TEM-energy dispersive spectroscopy (EDS) of the rGO-ZnO nanocomposite.

Zn2þ þ 2 OH
$ ZnðOHÞ2 while the growth is more favours happens along the [0 0 0 1] direc-
tion. The end planes for these ZnO crystals are generally reported
to be Zn terminated (0 0 0 1) surface [27].
ZnðOHÞ2 $ ZnO þ H2 O
The thermal energy required was less for the synthesis of ZnO 3.4. Photocatalytic dye degradation of the MO by the rGO-ZnO and the
and rGO-ZnO nanocomposite with the usage of microwave heating. ZnO nanocomposite
Since GO was added to obtain rGO along with the ZnO nanorod
synthesis during microwave heating, the growth mechanism for The photocatalytic ability of the ZnO and the rGO-ZnO is evalu-
the nanocomposite growth is completely different from the con- ated by the degradation of the methyl orange (MO) under UV irra-
ventional reported mechanisms for either ZnO nanorods or rGO. diation. The absorption spectra of the MO with the rGO-ZnO and
Microwave primarily interacts with the polar molecules such as the ZnO are recorded at every 20 min. The reduction in intensity
H2O to generate heat [56]. These molecules absorb microwaves of absorption peak from MO is depicted in Fig. 6a. The graph of
which results in rotational molecular motion and heating [57]. the concentration changes (Cf/Co) against time is plotted, as shown
The rapidly changing electromagnetic field in the microwave in Fig. 6b. It can be observed that the degradation of MO molecules
chamber causes the movement and polarization of the ions. This was considerably faster in presence of the rGO-ZnO catalyst in
phenomenon results in transient and localised high temperature comparison to that with ZnO catalyst. With rGO-ZnO nanocompos-
for the reaction system, which facilitates the growth and formation ite almost 98.23% of the MO dye was degraded within 60 min,
of the rGO anchored ZnO nano crystals. Prolonged heating during whereas, bare ZnO catalyst resulted in degradation of only
conventional processing usually results in the growth of the large 57.78%. The greater rate of degradation of MO molecules was
crystals. The microwave generates heat within the material and attributed the presence of rGO in rGO-ZnO. The rGO present in
also assists in the molecular motion, which increases the growth the rGO-ZnO composite provides higher surface area to bind MO
kinetics. The activation barrier to nucleation requires lesser ther- molecules through P-P conjugation with the offset along face-
mal energy than conventional heating. As a result, nucleation is to-face direction [59]. The conduction and valence band of ZnO is
favoured while the growth is restricted mainly due to less time at
4.05 eV and
7.25 eV, respectively (measured in vacuum).
at high temperatures and much finer crystals can form. It is known The work function of the graphene is
4.42 eV [60,61]. In such
that the ZnO has hexagonal lattice structure and the molecule is case, the ZnO in the rGO-ZnO transfers the photoelectrons from
polar in nature. The ZnO crystals grow along the c-axis of the the conduction band to the rGO to attract the MO molecules which
hexagonal lattice [58]. The inherent asymmetry along the c-axis enhances the photocatalytic ability of the rGO-ZnO [62]. The the-
leads to the anisotropic growth of the ZnO crystallites. Addition- ory behind high degradation rate is explained as following. When
ally, GONs provide the necessary seed for the nucleation to happen, the rGO-ZnO nanocomposite is exposed to UV light, ZnO emits
 S. Meti et al. / Applied Surface Science 451 (2018) 67–75 73

Fig. 6. (a) The absorbance spectra of the MO aqueous solution in the presence of the rGO-ZnO composite after different irradiation time, (b) Photocatalytic degradation of the
MO aqueous solution in presence of the rGO-ZnO and the ZnO and (c) the catalytic performance of rGO-ZnO for four successive cycles.

photoelectrons and holes in the water medium [33,63]. The photo- has enhanced the photocatalytic ability of the ZnO by more than
generated electrons then react with surface oxygen on the ZnO to 3.5 times. A higher rate constant is achieved by using the GO syn-
form superoxide radicals (O
2 ). The recombination of photogener- thesized by Hydrothermal method in comparison with the GO by
ated holes and surface oxygen generates hydroxyl radicals (OH
) Hummer’s method [66]. The performance of the rGO-ZnO
[64]. These active oxygen species (O


2 and OH ) are responsible for nanocomposite has also been compared with the rGO-ZnO
degrading the MO dye. They react with MO molecules to form CO2, nanocomposite synthesized, using ZnCl2 as precursor for ZnO. It
H2O and other byproducts. These active species can also recombine was found that after 60 min only 78.93% MO conversion was
within the catalyst without reacting with the MO. Therefore, the achieved in the case of rGO-ZnO catalyst where Zn(NO3)2 was used
active species must be accepted and delivered away to resist the as precursor. The detail of the experiment is explained in the
recombination of the photoelectrons and the holes. This role is taken supplementary information section (S1). The GO synthesized by
care by the rGO, which offer access to accept and transfer the photo- Hummer’s method was used in the preparation of rGO-ZnO
electrons. The effective charge transfer can reduce the charge recom- nanocomposite. The photocatalytic performance of such rGO-ZnO
bination and increase the photocatalytic activity of the rGO-ZnO (where GO prepared by Hummer’s method) is also compared. It
nanocomposite. Another important factor for increase in the photo was observed that the case of rGO-ZnO where GO was synthesized
degradation rate is the possibility of ZnO nanostructure and rGO using Hummer method, only 95.83% MO conversion was
sheets to connect each other very tightly [43]. The Fig. 6c shows achieved. The details can be found in supplementary information
the recycling ability and degradation performance of the rGO-ZnO section (S2).
nanocomposite. The graph depicts that the recycled nanocomposite
photocatalytic performance was almost same as that of the fresh cat- 4. Conclusions
alyst. Only, negligible decrease (only 2.58%) was seen in the perfor-
mance even after fourth cycle. The present work successfully demonstrated the use of
The photodegradation rates are calculated using pseudo first hydrothermally synthesized GONs in the preparation of rGO-ZnO
order kinetics using Langmuir-Hinshelwood model [65] nanocomposite. The hydrothermal method of GONs synthesis can
replace the conventional Hummer’s method where harmful chem-
Co
¼ ekt ð3Þ icals such as KMnO4, H2SO4, HCl etc. are used. Using microwave
Cf
energy, the ZnO nanoparticles and rGO-ZnO nanocomposite were
The rate constants for the rGO-ZnO and the ZnO calculated from synthesized in much shorter time periods (of order of 10 min)
the above equation are 0.0523 min
1 and 0.0143 min
1, respec- compared to conventional methods which requires hours, reducing
tively. It is found that the addition of the rGO content to the ZnO thermal budgets. Presence of the rGO in the rGO-ZnO was
74 S. Meti et al. / Applied Surface Science 451 (2018) 67–75

qualitatively and quantitatively analyzed by using XPS, Raman [16] J.A. Kellar, J.M.P. Alaboson, Q.H. Wang, M.C. Hersam, Identifying and
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