Accepted Manuscript

Title: Ultrasound assisted synthesis of ZnO/reduced graphene

oxide composites with enhanced photocatalytic activity and
anti-photocorrosion

Author: Yonggang Peng Junling Ji Dajun Chen

PII: S0169-4332(15)01883-8
DOI: http://dx.doi.org/doi:10.1016/j.apsusc.2015.08.070
Reference: APSUSC 31017

To appear in: APSUSC

Please cite this article as: Y. Peng, J. Ji, D. Chen, Ultrasound assisted
synthesis of ZnO/reduced graphene oxide composites with enhanced
photocatalytic activity and anti-photocorrosion, Applied Surface Science (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.08.070

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 Ultrasound assisted synthesis of ZnO/reduced graphene oxide composites with
enhanced photocatalytic activity and anti-photocorrosion

Yonggang Peng a,b,*, Junling Ji a,Dajun Chen c

a
Institute of Petrochemical Technology, Changzhou University, Changzhou

t
ip
213164,China
b
Jiangsu Province Key Laboratory of Fine Petrochemical Engineering,Changzhou

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University, Changzhou 213164, China

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c
State Key Laboratory for Modification of Chemical Fibers and Polymer Materials,
College of Material Science and Engineering, Donghua University, Shanghai 201620,
P.R. China an
Correspondence to: Yonggang Peng;
M
Tel: +86 519 8633 0256
E-mail: pengyonggang@126.com
e d

Abstract:A method to improve the photocatalytic activity and suppress the

pt

photocorrosion of ZnO was developed by depositing ZnO nanoparticles onto the surface
of reduced graphene oxide (rGO) via in situ growth with ultrasound assisted synthesis.
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The optimum synergetic effect of ZnO/rGO composite was found at a weight ratio of
2%(rGO/ZnO). Compared with ZnO, the photocatalytic activities of ZnO/rGO composite
Ac

for the degradation of methylene blue (MB)and C.I. acid red 249 (AR249) aqueous
solutions under UV light irradiation were increased by 8.6% and 14.7%, respectively. The
improved photocatalytic activity was originated from the rapid separation of
photogenerated electrons and holes on the interface of rGO and ZnO. The photocorrosion
of ZnO was inhibited obviously after hybridization with rGO. Even after six successive
cycles under UV irradiation, the photocatalytic activities of ZnO/rGO composite for MB

Page 1 of 20
and AR249 still retained 92.9% and 94.8% of that for the first cycling run,while that of
ZnO obviously decreased due to serious photocorrosion.The photocorrosion inhibition of
ZnO by rGO was attributed to the reduced activation of surface oxygen atom on the
surface of ZnO.

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Keywords: ZnO; ultrasound-assisted synthesis; reduced graphene oxide; diethylene

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glycol; photocatalysis

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1 ZnO/reduced graphene oxide composites were prepared by in situ growth with

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ultrasound assisted method.
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2 A plausible formation mechanism of ZnO/rGO composites was deduced.

3 After hybridization with rGO,the photocatalytic activity of ZnO was improved and its
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photocorrosion was inhibited obviously.
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1.Introduction
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ZnO, as an important semiconductor with a wide band gap of 3.37 eV and a large
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excition binding energy of 60 meV,exhibits a higher efficiency than TiO2 in

photocatalytic degradation of some dyes in water and photoelectric conversion[1-2].

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However, the quick recombination of photogenerated electron-hole pairs, poor response

to solar light and the photocorrosion have hindered the application of ZnO in

photocatalysis. In order to improve its photocatalytic activity and inhibit its

photocorrosion, several conductive materials, such as monolayer polyaniline[3],

C3N4[4] ,C60[5] etc.,were used to hybridize with ZnO.

Page 2 of 20
 Graphene,a new two-dimensional allotrope of crystalline carbon, possesses exceptional

electron-transport property, huge specific surface area and high chemical

stability[6-8].Many graphene composites, such as ZnO/graphene oxide (ZnO/GO)

t
[9,10],ZnO/Carbon Nanotube/rGO[11],TiO2/GO[12],CuS/rGO nanocomposites[13],and

ip
In2S3 nanosheets/graphene[14] etc., have been synthesized. Conventional mixing,

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hydrothermal and solvothermal method can be used to prepare graphene composites[15].

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However, the restacks of the exfoliated GO or rGO sheets and the aggregation of

nanoparticles lead to the decrease of the properties of graphene composites .

an
Nowadays sonochemistry has been proven to be an effective way for the synthesis of

inorganic nanoparticles/graphene composites[16-17].When liquids are treated with

M
ultrasonic irradiation, acoustic cavitation, i.e., formation, growth and immediate collapse
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of bubbles in the liquid results in forming high temperature, high pressure and extremely
e

rapid cooling rates[18].Such extreme chemical environments lead to the formation of

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smaller sized inorganic particles. Further the ultrasonication is advantageous to reducing

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the agglomeration of nanoparticles and the restacks of the exfoliated graphene sheets[19].

Hence in this paper, a facile one-step sonochemical approach was followed to prepare
Ac

ZnO/rGO composite. The structure and morphology of the products were characterized

by Fourier-transform infrared spectra (FTIR), X-ray diffraction (XRD), transmission

electron microscopy (TEM) ,X-ray photoelectron spectra (XPS) and Raman spectra. The

formation process of ZnO/rGO composites was proposed and discussed. Finally, the

photocatalytic activity and photostability of the as-prepared products were investigated

Page 3 of 20
by monitoring the degradation of methylene blue (MB) and C.I. Acid Red 249 (AR249)

under UV irradiation.

2. Experimental

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2.1. Materials

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Zinc acetate dihydrate (Zn(CH3CO2O)2.2(H2O)), diethylene glycol (DEG) were

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purchased from Sinapharm Chemical Reagent Co.,Ltd. C.I. Acid Red 249

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(disodium3-[(5-chloro-2-phenoxyphenyl)azo]-4-hydroxy-5-[[(p-tolyl)sulphonyl]

amino]naphthalene-2,7-disulphonate, molecular formula C29H20ClN3Na2O10S3 and

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molecular weight 747.5) was obtained from local dye suppliers, and the structure of

AR249 was shown in supplementary data. All the chemicals were used without further
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purification.
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2.2. Preparation of ZnO/rGO composites

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GO was prepared from natural graphite by a modified Hummer’s method.[20-21].The

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purified GO was dispersed in 40 mL diethylene glycol (DEG) and sonicated

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(40KHz,500W) for 1 h under ambient condition to give a brown dispersion. Then 3.512 g

(16mmol) zinc acetate dihydrate was added to the brown dispersion under magnetic
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stirring. After the dissolution of zinc acetate dihydrate, the dispersion was treated with an

ultrasonic T-horn (Manufactured by Nanjing Xian’ou Instrument Co. Ltd., China) at

480W of dissipated power for 2 h on 2 s pulse mode (2 s on mode and 2 s off mode). The

titanium tip of the horn was located at the center of the solution and immersed 1 cm deep

in it. The obtained product was centrifuged, washed by absolute alcohol and distilled

Page 4 of 20
water for several times. The resulting product was dried under vacuum at 80℃.According

to the weight ratio between GO to ZnO theoretically, ZnO/rGO composites with ratio of

100:1,100:2,and 100:3 were denominated as ZnO/rGO01,ZnO/rGO02,ZnO/rGO03.

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ZnO was prepared in the same procedure as that of ZnO/rGO composites except that

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GO was not added.

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2.3. Characterization methods

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Fourier-transform infrared spectra of the samples were recorded by PROTÉGÉ 460
spectrophotometer (Nicolet, USA). X-ray pattern of the products were obtained using

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power X-ray diffraction at room temperature on a Panalytical X-pert diffractometer with
Cu Kαradiation (λ=0.154 nm), running at 40 kV and 30 mA, scanning from 5° to 80
° at 3°/min. Transmission electron microscopy analyses were taken with a JEOL
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JEM-2100 microscope with an acceleration voltage of 300 kV. Raman spectra were
recorded from 400-2000cm-1 on a Renishaw Invia Raman spectronmeter using a 514.5nm
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argon ion laser. X-ray photoelectron spectra (XPS) were recorded by employing Thermo
e

ESCALAB 250 with Al Kα(hv=1486.6eV) as X-ray source. The UV-vis diffuse

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reflectance spectra of the prepared samples were recorded in the wavelength range from
200 to 800 nm using a Varian Cary 100 Scan UV-vis system equipped with an integrating
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sphere attachment (USRS-99-010) as a reflectance standard.

2.4. Photocatalytic activity test

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The photocatalytic activity of synthesized ZnO/rGO composites was evaluated by the

degradation of MB and AR249 under UV irradiation at room temperature. A 15 W UV

lamp (Beijing Lighting Research Institute, with peak emission at λ=365 nm) was used

as UV light. Prior to irradiation, the suspension containing dyes and photocatalyst was

Page 5 of 20
magnetically stirred in a dark condition for 1 h until the adsorption equilibrium was

established.

In all the experiments, 50 mL of 50 mg/L dye solution containing 50 mg photocatalyst

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was irradiated under the ultraviolet light lamp maintaining the distance between the light

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source and the surface of the suspension about 10 cm. At the given time intervals, 2 mL

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of the suspension was taken out and centrifuged at 10000 rpm for 10 min to remove the

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catalyst particles completely. The concentration of solution was analyzed by measuring

the absorbance at λmax with a UV-vis spectrophotometer.

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To assess the photocatalytic stability, the photocatalyst was collected after the first

cycle of photocatalytic test, and washed with deionized water for many times, dried at 80
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℃ for 12 h. Then, another photocatalytic degradation cycle for fresh dye solution was
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operated with the recycled ZnO/rGO composite as photocatalyst.

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3. Results and discussion

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3.1 XRD analysis

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The XRD patterns of the as-prepared ZnO/rGO composites are shown in Fig. 1.As Fig.

1a shown, the peaks of all the three samples with different weight addition ratios of GO
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are similar to that of the hexagonal phase wurtzite ZnO (JCPDS No. 36-1451). The main

peaks at 2θ=31.7°, 34.4°,36.2°,47.5°,56.5°,62.8°,67.9°,69.0°are ascribed to

the (100), (002), (101), (102), (110), (103), (112) and (201) crystalline planes of wurtzite

ZnO. And no characteristic peaks related to GO or rGO are detected. This is because GO

was reduced and exfoliated during the preparation of ZnO/rGO composites (Fig.1b), and

Page 6 of 20
the assembled high-crystallized ZnO on the rGO planes prevented the face-to-face

regular restack of rGO [22].

3.2 FTIR spectroscopy

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Fig.2 shows FTIR spectra of GO, rGO and ZnO/rGO composite. In Fig.2a,the peaks of

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GO appeared at 3412.7 cm-1,1738 cm-1,1628 cm-1,1384.4 cm-1,1077.1 cm-1 are

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correspond to O-H stretching vibrations of absorbed H2O molecules, C=O stretching

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vibrations of -COOH groups situated at the edges of GO sheets, skeletal vibrations of

unoxidized graphitic domains, O-H deformations of the C-OH groups, C-O-C vibrations,
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respectively. In the spectrum of rGO, the characteristic peaks of C-O-C and C=O

obviously turn weak or disappear (Fig. 2b), and a new absorption peak appears at
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1579cm-1 (Fig. 2b). These show GO has been reduced during sonication process.
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3.3 Raman spectroscopy

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Raman spectrum is a well-known sensitive tool for studying the ordered/disordered

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crystal structures of carbonaceous materials. Fig.3 shows the Raman spectra of GO, rGO
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and ZnO/rGO02 composite. The raman spectrum of GO exhibits two major peaks at 1350

cm-1 (D band) and at 1596cm-1 (G band), which are usually assigned to the breathing
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mode of K-point phonons of A1g symmetry and the E2g phonon of sp2 bonds of carbon

atoms, respectively.The D band and G band are also observed in the Raman spectra of

rGO and ZnO/rGO02 composite. But the intensity ratio of ID/IG increases from 0.94 to

1.07, which shows that more sp2 domains (graphene sheets) have formed and the GO has

been reduced[23].

Page 7 of 20
3.4 XPS analysis

The reduction of GO to rGO is further confirmed by the XPS spectra (Fig.4a-c). The

survey spectrum shows the presence of three dominative elements: C, Zn, O. The

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deconvoluted XPS C1s spectrum exhibits rGO with three main components that

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corresponds to the carbon atoms in different functional groups: the nonoxygenated C-C

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bond (284.8 eV), the C-O bond of epoxy and hydroxyl (286.1eV) and the carbonyl C=O

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(288.6eV).The peak at 283.3 eV can be assigned to the C-M bond (Fig. 4b), which

indicates that the bond between C and Zn has formed during the process of ultrasonic
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irradiation [24].Compared with GO, the relative area percentage of the nonoxygenated

C-C bond increases and that of the C-O bond of epoxy and hydroxyl decreases (As
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shown in Table 1), which deduces the reduction of GO took place[25-26]. This result is
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consistent with that of FTIR and XRD data. The peak positions of Zn 2p1/2 and 2p3/2 in
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the ZnO/rGO composite are consistent with the standard values and those of ZnO
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nanoparticles alone[27] (Fig. 4c), which further proves that the Zn exists mainly in the
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Zn2+ state in both the ZnO nanoparticles and in the ZnO nanoparticles supported on the

rGO sheets[28].
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3.5 Transmission electron microscopy

The direct evidence of the formation of ZnO nanoparticles on the planes and edges of

rGO sheets is given by TEM in Fig. 5. The two-dimensional graphene sheets with

wrinkles is clearly observed, and ZnO nanoparticles with an average size of 10-20 nm are

distributed randomly on the rGO sheets. During the preparation process of ZnO/rGO

Page 8 of 20
composites, Zn2+ was firstly captured by carboxylate anions on the GO by coordination;

and ZnO nanoparticles were deposited in situ on GO sheets. The presence of GO in the

system serves as a hard template to limit the growth and agglomeration of ZnO[17].In

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addition, the narrow size distribution is ascribed to the micromixing and turbulence

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generated during ultrasonic irradiation[19].

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3.6 Preparation process of ZnO/rGO composites

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Based on all the above results, the process for preparation of ZnO/rGO composites is

given in Fig. 6. There are many oxygen-containing groups bound on the surface of GO.
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When Zinc acetate was mixed with GO, these positive Zn2+ ions would adsorb onto the

surface of GO sheets owing to the electrostatic attraction.Under the acoustic cavitations,

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the Zn2+ ions adsorbed on the surface of GO sheets formed in situ ZnO nanoparticles.
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Simultaneously, GO was reduced to rGO [29], and rGO sheets were exfoliated. Due to
e

the existence of ZnO nanoparticles, the restack of exfoliated rGO sheets was prevented.
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3.7 UV-vis Diffuse Reflectance Spectra

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Fig.7 displays the UV-vis diffuse reflectance spectra of ZnO and ZnO/rGO composites.

As expected, ZnO shows the characteristic spectrum with its fundamental absorption
Ac

sharp edge rising at 400 nm. The absorption edge of the ZnO/rGO composites remains

the same as that of pure ZnO, which indicates that the band gap has not been changed.

However, the absorption intensity of ZnO/rGO composites increases with the increasing

of the rGO amount, it can be ascribed to the increase in surface electric charge of ZnO

within the composites due to the introduction of rGO.

Page 9 of 20
3.8 Photocatalytic activity of ZnO and ZnO/rGO composites

The photocatalytic performance of ZnO and ZnO/rGO composites was evaluated by

the degradation of MB and AR249 under UV irradiation. As shown in Fig. 8, it was clear

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that the absorbent capacity of ZnO/rGO02 composite toward MB and AR249 was

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stronger than that of the bare ZnO, which was because rGO offered large surface area to

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bind MB and AR249 molecular through the π-π conjugation with offset face-to-face

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direction. It was observed that MB and AR249 were very stable under UV irradiation in

the absence of the photocatalyst. After 120 min of UV irradiation, the photolysis
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efficiency of the two dyes were very low. When different photocatalysts were added, the

photocatalytic degradation efficiency of MB and AR249 followed the order ZnO/rGO02

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＞ZnO/rGO03＞ZnO/rGO01＞ZnO, which demonstrated all the ZnO/rGO composites
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exhibited much higher photocatalytic activities than the bare ZnO. Clearly, the
e

photocatalytic activity was improved gradually with the increasing proportion of rGO.
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When the proportion of rGO reached 2%, the photocatalytic activities of ZnO/rGO
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composite for the degradation of methylene blue (MB)and C.I. acid red 249 (AR249)

aqueous solutions under UV light irradiation were increased by 8.6% and 14.7%,
Ac

respectively. With the excess amount addition of rGO, the photocatalytic performance

decreased. Thus, it could be concluded that the addition of an appropriate amount of rGO

could improve the photoactivity effectively. This should be attributed to the following

reasons. The introduced rGO enhanced the absorption capacity of dyes molecular,

promoted the separation of photogenerated electrons and holes and suppressed the

Page 10 of 20
photocorrosion of ZnO. However, the excess addition amount of rGO increased the

opacity and light scattering. In other words, the introduction of the excess addition

amount of rGO resulted in shielding of the active sites on the catalyst surface and

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decreased the intensity of light through the depth of the reaction solution[30].

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3.9 Photostablity of ZnO and ZnO/rGO composites

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In order to investigate the photostablity of the photocatalysts, recycling experiments of

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ZnO and ZnO/rGO02 composite were performed (As shown in Fig. 9).Under 120 min

UV irradiation, the photodegradation efficiency of MB and AR249 in the presence of

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ZnO were 87.4% and 78.6%, respectively. With the increase of recycle times, the

photocatalytic activity of ZnO under UV irradiation became worse and worse. After six
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recycles, only 63.4% and 50.2% of MB and AR249 were degraded, which may be due to
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the photoinduced dissolution. Under UV irradiation, ZnO was emitted to generate photo
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electrons and holes. The holes were transfer to the solid-solution interface and reacted
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with oxygen atoms exiting as the unsaturated state on the surface of ZnO, which resulted
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in the escape of oxygen from the surface. Some photoinduced holes were consumed

during the photocorrosion process of ZnO, which led to the decrease photocatalytic
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activity. The photocorrosion process can be presented as follows[31]:

1
ZnO + 2h + + nH 2O ® Zn (OH )(2
n
-n )+
+ O 2 + nH +
2
Where n depends on the pH of the solution. After hybridization with rGO, the

activation of oxygen atoms on the surface of ZnO was reduced, and the photooxidation of

dyes molecules absorbed on the surface of rGO consumed part of the photogenerated

Page 11 of 20
holes, which effectively inhibited the photocorrosion of ZnO. After six successive cycles

under UV irradiation, the photocatalytic activity of ZnO/rGO02 composite for MB and

AR249 still retained 92.9% and 94.8% of that for the first cycling run.

3.9 Mechanism of enhanced photocatalytic activity and anti-photocorrosion

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In order to detect the main active oxidative species in the photocatalytic process and

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investigate the photocatalytic mechanism of ZnO/rGO02 composite, the trapping

experiments of radical and holes were performed (As shown in Fig. 10).The addition of

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50mM 1-butanol (1-BuOH) as hydroxyl radicals scavenger led to a slight decrease of the
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photcatalytic degradation of MB and AR249. When 50mM isopropyl alcohol (IPA) as

holes scavenger was added, the photodegradation of the two dyes was obviously inhibited,
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which suggested that direct hole oxidation was the main active oxidative species. This
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result was in agreement with previous study [32].

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According to the results of photodegradation and photogenerated carrier trapping test,

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a proposed schematic mechanism for photocatalytic degradation of MB and AR249 over

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ZnO/rGO composite is summarized in Fig.11.

Under UV irradiation, ZnO was excited to form the photogenerated electrons and holes.
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Due to the interfacial contact between ZnO and rGO, the photogenerated electrons

transferred to rGO, which inhibited the recombination of electron-hole pairs and

increased the separation of photogenerated charge. The holes left in the valence band

could either react with adsorbed water (or surface hydroxyl) to form hydroxyl radicals or

directly oxidize organic dyes. The enhancement of charge carrier separation improved the

Page 12 of 20
photocatalytic activity of ZnO/rGO composite. The reaction between photogenerated

holes and adsorbed water or dyes on the surface of rGO hindered the photocorrosion of

ZnO.

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4.Conclusions

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ZnO/rGO composites were prepared via a facile ultrasound treatment of GO

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dispersion using DEG as solvent in the present of zinc acetate dihydrate. XRD and TEM

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demonstrated the formation in situ of ZnO on the surface of rGO sheets. FTIR,XPS and

Raman spectra showed GO was reduced to rGO. The probable reaction mechanism for
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preparation of ZnO/rGO composites was proposed. Photocatalytic experiments showed

the optimal rGO content for ZnO/rGO composite was 2%. And ZnO/rGO composites
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exhibited higher photocatalytic activity and photo stability than the bare ZnO to the
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degradation of MB and AR249 under UV irradiation, which was attributed to the higher
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separation efficiency of electron-hole pairs caused by the rapid photogenerated charge

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separation.
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Acknowledgments

This work was supported by the Jiangsu Province Key Laboratory of Fine
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Petrochemical Engineering (KF1305), the doctoral fund of Changzhou University

(ZMF14020065) and the project of Huai’an patent transformation (HAZ201415).

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Fig.1a XRD patterns of (a)ZnO/rGO01;(b)ZnO/rGO02;(c) ZnO/rGO03

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Fig.1b XRD patterns of (a) GO; (b) rGO( rGO was obtained by treating the brown

dispersion of GO with an ultrasonic T-horn at 480W of dissipated power for 2 h on 2 s

pulse mode in the absence of zinc acetate dihydrate.)

Fig.2a FTIR spectra (4000-380cm-1) of (a)GO; (b)rGO; (c)ZnO/rGO02

Fig.2b FTIR spectra (2000-1000cm-1) of (a)GO; (b) rGO; (c) ZnO/rGO02

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Fig.3 Raman spectra of GO,rGO and ZnO/rGO02 composite

Fig.4 (a)Surver XPS, (b)deconvoluted XPS C1s,(c)deconvoluted XPS Zn2p spectra of

ZnO/rGO02 composite

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Fig.5 TEM image of ZnO/rGO02 composite

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Fig. 6 Process for preparation of ZnO/rGO composites

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Fig. 7 UV-Vis diffuse reflectance spectra of (a) ZnO/rGO03 composite;(b) ZnO/rGO02

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composite; (c)ZnO/rGO01 composite;(d)ZnO

Fig. 8a Photodegradation of MB by ZnO and ZnO/rGO composites under UV

irradiation
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Fig. 8b Photodegradation of AR249 by ZnO and ZnO/rGO02 composites under UV
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irradiation
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Fig.9a Effect of recycle times on the degradation of MB over ZnO and ZnO/rGO02
e

composite
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Fig. 9b Effect of recycle times on the degradation of AR249 over ZnO and ZnO/rGO02
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composite

Fig. 10a Effect of IPA and 1-BuOH addition on the photodegradation of MB by

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ZnO/rGO02 composite

Fig. 10b Effect of IPA and 1-BuOH addition on the photodegradation of AR249 by

ZnO/rGO02 composite

Fig. 11 Schematic diagram of photodegradation of dyes using ZnO/rGO composite as

photocatalyst

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Fig. S1. The structure of AR249

Table 1 XPS data of ZnO/rGO02 composite: binding energies and relative area

percentages (in parentheses)

Sample C=O / eV C-O / eV C-C / eV C-M / eV

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ZnO-GO 288.6(10.5%) 286.1(17.1%) 284.8(62.1%) 283.3(10.3%)

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