Journal of Alloys and Compounds 623 (2015) 298303

Contents lists available at ScienceDirect

Journal of Alloys and Compounds

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

Facile hydrothermal synthesis of TiO2 nanospindles-reduced graphene

oxide composite with a enhanced photocatalytic activity
Huitong Wu a, Jun Fan a,, Enzhou Liu a, Xiaoyun Hu b, Yongning Ma a, Xiao Fan a, Yinye Li a, Chunni Tang a
a
School of Chemical Engineering, Northwest University, Xian, Shanxi, China
b
School of Physics, Northwest University, Xian, Shanxi, China

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

Article history: In this study, the hydrothermal method was used to synthesize TiO2 nanospindle which are featured by
Received 8 August 2014 large exposed {0 0 1} facets and then fabricate TiO2 nanospindle/reduced graphene oxide nanocomposite
Received in revised form 11 October 2014 (TiO2/RGO). Graphene oxide (GO) was prepared via improved Hummers method. GO reduction to RGO
Accepted 26 October 2014
and hybridization between TiO2 nanospindle and RGO by forming chemical bonding was achieved in a
Available online 1 November 2014
facile hydrothermal process. The as-prepared composites were characterized by X-ray diffraction
(XRD), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), scanning
Keywords:
electron microscope (SEM), transmission electron microscopy (TEM), photoluminescence spectrum (PL),
Reduced graphene oxide
TiO2 nanospindle
UVVis absorption spectrum (UVVis) and Raman spectrum, respectively. The photocatalytic activity was
Composite materials evaluated by the photodegradation of methylene blue (MB). The prepared TiO2/RGO nanocomposite
Photocatalytic activity has superior photocatalytic activity in the degradation test, showing an impressive photocatalytic
Hydrothermal enhancement over pure TiO2 nanospindle which because graphene worked as the adsorbent and electron
acceptor to efciently enhance the dye photodecomposition.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Titanium dioxide (TiO2) is one of the most widely researched
semiconducting metal oxides and has been widely applied in the
environment science owing to its signicant advantages such as
low cost, nontoxity, chemical stability, and superior photoactivity
over other semiconductors that have been investigated [15]. In
recently years, tailored synthesis of anatase TiO2 toward highly
active facets has attracted much attention. Some studies have
demonstrated that {0 0 1} facets of anatase TiO2 nanocrystals exhi-
bit higher activities in photodegradation of organic pollutants than
{1 0 1} facets [6,7]. Usually, the active {0 0 1} facets are easier to be
exposed on two-dimensional nanosheets than on other morpholo-
gies [8,9]. Zhao et al. [10] had fabricated anatase TiO2 nanospindles
which are featured by large exposed {0 0 1} facets and found they
provided a good solution to the problems of poor electron trans-
port and severe aggregation of TiO2 nanoparticles.
In general, one main drawback of the TiO2 nanostructures is
that the photo generated electronhole pairs have faster recombi-
nation rates than the rate of chemisorption between TiO2 and pol-
lutants, which will reduce the photocatalytic efciency of TiO2. To
Corresponding author at: School of Chemical Engineering, Northwest Univer-
sity, No. 229 Taibai North Road, Xian, Shanxi 710069, China.
E-mail address: fanjun@nwu.edu.cn (J. Fan).
prevent this recombination, there are many other methods have
been used to elevate the photocatalytic efciency of TiO2, such as
compositing TiO2 with noble metals, metal oxides, semiconductors
and carbonaceous materials [1115]. Among those, combining
TiO2 with carbonaceous materials recently attracted a lot of atten-
tion owing to its excellent properties.
Graphene, a new class of carbonaceous material comprising sin-
gle-atom-thick sp2 hybrid carbon atoms, has attracted much atten-
tion owing to its several intriguing properties, such as electron
mobility, thermal conductivity, high values of surface area, and
mechanical strength [1620]. Moreover, the graphene has great
surface properties which can be chemically modied with func-
tional groups such as hydroxyl, carboxyl, epoxy or other organic
groups which is promotive for its use in composite materials [21].
There have been several reports highlighting the improvements
in photocatalytic activity of TiO2 nanoparticle-reduced graphene
composites than that of TiO2 nanoparticles alone [22,23,16,24].
Despite these promising results, the TiO2 nanoparticles tend to
agglomerate and have poor interfacial contact with the graphene
surface because of the nanoparticles nearly spherical shape. There-
fore, a form of TiO2 that provides maximum interfacial contact
with graphene surface without aggregating is an essential factor
for improving the photocatalytic performance of grapheneTiO2
composites. In contrast to TiO2 nanoparticles, TiO2 nanospindles
have much higher electron transport and less aggregation as we

http://dx.doi.org/10.1016/j.jallcom.2014.10.153
0925-8388/ 2014 Elsevier B.V. All rights reserved.
 H. Wu et al. / Journal of Alloys and Compounds 623 (2015) 298303 299

mentioned before, so we are planning to report a TiO2-reduced 3. Results and discussion

graphene oxide composite photocatalyst by the coating of anatase
TiO2 nanospindles onto the surface of RGO, which showed a
promising combination due to the chemical bonding between
RGO and TiO2 nanospindles. Most importantly, the composite
preform a better photocatalytic activity.
2. Experimental section
2.1. Synthesis of graphite oxide
GO was synthesized via modied Hummers method [2527]. In detail, 3 g of
graphite was added into a mixture of 2.5 g of K2S2O8, 2.5 g of P2O5, and 12 ml of con-
centrated H2SO4 and kept owing for 24 h in oil bath at 85 C. Then wish it with
deionized water for several times until the pH value was equal to 7. We call it
pre-oxidized graphite. Then, 1 g pre-oxidized graphite was put into a mixture of
92 ml concentrated H2SO4, 24 ml HNO3 and 6 g KMnO4. The solution was rst kept
stirring for 2 h in ice-bath. Then, heated the solution to 35 C in water bath and
maintained 1 h. After being heated to 80 C and kept stirring for 0.5 h, 300 ml deion-
ized and 20 ml 30% H2O2 solution was added slowly into the solution when it
became yellow. By centrifugally separated repeatedly with deionized water until
the pH of the ltrate was neutral, the graphite oxide was obtained by drying at
65 C for 4 h.
2.2. Synthesis of TiO2 nanospindle
In a typical synthesis [28], 1.00 ml of deionized water was added to 30 ml of iso-
propyl alcohol (IPA) with 10 min of stirring. A 0.15 ml volume of diethylenetriamine
(DETA) was added to the above solution with 10 min of stirring. Then, 1.00 ml of
titanium isopropoxide was added. After stirring for 30 min, the white reaction solu-
tion was transferred into a 50 ml Teon-lined autoclave. Subsequently, the auto-
clave was kept at 180 C for 24 h in an oven. Then the products were separated
by centrifugation, washed with deionized water and ethanol. After being recovered
by vacuum ltration, the wet products were baked at 60 C for 8 h. the white-color
anatase TiO2 nanospindle powder was obtained.
2.3. Synthesis of TiO2 nanospindle/graphene
The hydrothermal method was employed to synthesize the TiO2 nanospindle-
reduced graphene oxide hybrid nanostructures. 0.05 g GO was dissolved into a mix-
ture of 60 ml deionized water and 30 ml ethanol with sonicating 2 h to exfoliate the
GO thoroughly, and the transparent solution namely Graphene Oxide was obtained.
0.95 g of as-made TiO2 nanospindle was added slowly to the GO dispersions while
stirring. Then the sonication was employed for 1 h until a homogeneous suspension
was achieved, which shows a uniform light gray color, and the suspension was trans-
ferred to a Teon-lined autoclave of 100 ml capacity and maintained at 180 C for
12 h to synthesize the composite of TiO2/RGO, and reduction of GO was also realized
during this process with ethanol as the active agent, then be cooled down to room
temperature, By centrifugally separated repeatedly with deionized water, the
TiO2/RGO(5%) was obtained by drying overnight at 65 C. For comparison, TiO2/
RGO(10%) and TiO2/RGO(15%) were obtained by the same process.
2.4. Characterization
Fig. 1 shows XRD patterns of GO, TiO2 nanospindle and TiO2/
RGO(5%). From Fig. 1a we can see the XRD pattern of GO with a
characteristic (0 0 2) peak at 2h = 10.5. Compared to GO, complete
disappearance of the strong (0 0 2) peak in TiO2/RGO composites
suggests successful conversion of GO to reduced graphene oxide
in the nal composites. The reections in the XRD pattern of the
TiO2 nanospindle (shown in Fig. 1b) can be indexed to pure anatase
phase of TiO2 (JCPDS Card No. 21-1272) and no characteristic peaks
of impurities have been detected. The narrow and sharp peaks sug-
gest that the product is crystalline. For composites, the (1 0 1) peak
is much broader than that of TiO2 nanospindle. Peak broadening
suggest that the lattice structure of TiO2 is distorted by the interac-
tion with RGO. Which may result from the main characteristic peak
of graphene at 24.5 might be shielded by the main peak of anatase
TiO2 at 25.3. It also proves GO reduce to the RGO.
Raman spectra of TiO2 nanospindle and TiO2/RGO(5%) was
displayed in Fig. 2. The major Raman bands at 147, 199, 399, 515
and 639 cm 1 can be attributed the ve Raman-active modes of
anatase phase TiO2 with the symmetries of Eg, Eg, B1g, B1g and Eg,
respectively. Compared to pure TiO2, TiO2/RGO (shown in Fig. 2b)
shows the typical features of graphene with the presence of D band
located at 1354 cm 1 and G band at 1594 cm 1. G band provided
information on the in-plane vibration of sp2 bonded carbon atoms
[29], while the D band was attributed to the presence of sp3 defects
in RGO [30]. This demonstrates that the RGO has been successfully
exfoliated and synthesized into the composite. To verify the num-
ber of graphene layers in the produced sample, we analyzed the
variation of the 2D band (see the inset). From the shape and inten-
sity of the 2D peak we can infer that the RGO sheets are multi-layer
[31,32].
Fig. 3 shows FTIR patterns of GO, TiO2 nanospindle, TiO2/RGO(5%)
and TiO2/RGO(5%)* (The composite was irradiated for 5 h). The peak
around 1726 cm 1 and 1078 cm 1 of GO was assigned to C@O
stretching of the COOH groups, which disappeared in TiO2/RGO, this
could be conrmed the reduction of GO. The peak 1375 cm 1 of
TiO2/RGO(5%) was assigned to C@O stretching of the carboxyl
groups [33,34], which was disappeared in TiO2/RGO(5%)*, this might
be due to that TiO2 can reduce the reduced graphene oxide into
graphene in an UV or visible light photocatalytic process [35,36].
Typically TiAOATi and TiAOAC bonds show low frequency bands
around 690 cm 1 and 798 cm 1 respectively. Therefore, the broad
band at the low frequency region in the composite can be considered
combination of TiAOATi and TiAOAC vibrations because of the
chemical interaction of TiO2 nanospindle with the RGO. In addition,

Sample morphology was observed by Hitachi S-4800 scanning electron micro-

scope and Tecnai G2 F20 S-TWIN transmission electron microscopy. Powder X-ray
diffraction patterns were recorded on a Shimadzu XRD-6000 X-ray diffractometer.
Fourier transform infrared spectra of the samples were recorded on a Bruker
spectrophotometer Vertex70. Photoluminescence spectra were measured by
Hitachi F-7000 uorescence spectrometer. X-ray photoelectron spectroscopy
(XPS) characterization was performed with an Kratos AXIS NOVA spectrometer,
UVVis Absorption spectra were obtained on a UV-3600 Shimadzu spectrophotom-
eter. The BrunauerEmmettTeller (BET) surface area of the photocatalyst sample
was measured by N2 adsorption Quantachrome NOVA 2000e. Raman spectra were
collected on a Renishaw inVia Reex Raman spectrometer.

2.5. Photocatalysis testing

The photocatalytic activities of TiO2/RGO were measured by the photodegrada-

tion of Mb and compared it with pure P25 and TiO2 nanospindle. The process of
degradation of Mb dye is typical, 10 mg of the as-prepared samples were suspended
in 60 ml of Mb aqueous solutions (10 mg/l). Before irradiation, the suspensions
were stirred in the dark for 1 h to establish an adsorptiondesorption equilibrium.
Then the above suspension was exposed to light irradiation by a 300 W xenon lamp.
A 3 ml solution was taken during the experiments every 5 min, and centrifuged
to remove the catalyst completely. The solution was analyzed by a UVVis
spectrophotometer. Fig. 1. XRD patterns of (a) GO, (b) TiO2 nanospindle and (c) TiO2/RGO(5%).
300 H. Wu et al. / Journal of Alloys and Compounds 623 (2015) 298303
Fig. 2. Raman spectra of (a) TiO2 nanospindle and (b) TiO2/RGO(5%). The insets
show the 2D peak of the composite.
Fig. 3. FTIR pattern of (a) GO, (b) TiO2 nanospindle, (c) TiO2/RGO(5%) and (d) TiO2/
RGO(5%).
the broad absorption from 3000 to 3700 cm 1 and 1625 cm 1 was
caused by the OAH stretching vibration of the surface hydroxyl
groups on TiO2 and GO.
The XPS spectra at the Ti(2p) binding energy region of TiO2/
RGO(5%) was showed in Fig. 4 indicates two peaks centered at
458.28 and 463.98 eV, assigned to Ti 2p3/2 and Ti 2p1/2, respec-
tively. The splitting between these two bands was 5.7 eV, indicat-
ing predominant formation of the normal state of Ti4+ in the TiO2 of
the composite. The peak deconvolution of the Ti(2p) spectrum
indicated two other weak peaks centered at 459.7 and 465.9 eV
(relating to the Ti(2p1/2) and Ti(2p3/2) peaks) which were attrib-
uted to formation of a TiAC bond on the composite surface [15,37].
From the SEM image in Fig. 5a, the as-prepared anatase TiO2
displays exclusively a spindle-like nanostructure with a uniform
size. More quantitatively, the diameters of 3050 nm and the
lengths of 100200 nm for the nanospindles can be estimated from
the TEM image in Fig. 5b. Fig. 5c is the HRTEM image of a randomly
chosen TiO2 nanospindle , and its corresponding partial image as
shown in Fig. 5d. The lattice fringes of TiO2 nanospindle can be
clearly observed, indicating that the nanospindle is single crystal-
line with good crystallinity. The lattice spacing of 3.5 and 4.8
can be indexed to the (1 0 1) and (0 0 1) planes of anatase TiO2,
Fig. 4. XPS spectra at the Ti(2p) binding energy region of TiO2/RGO(5%).
respectively. As seen in Fig. 5e, the GO successfully reduced to
the reduced graphene oxide and the TiO2 nanospindle occupy most
of the edge areas of RGO [38].
Fig. 6 shows the UVVis diffuse reectance spectra of TiO2
nanospindle and TiO2/RGO. Degussa TiO2 nanospindle displays an
absorption edge at about 400 nm. As we can see in Fig. 6bd, the
addition of RGO increases light absorption intensity in the visible
light regions compared to TiO2 nanospindle. The range of light
absorption plays an important role in the photocatalytic perfor-
mance. Extending light absorption from UV to visible light range
will allow more efcient utilization of the solar spectrum. At the
same time, light absorption extended to 420, 470 and 560 nm as
incorporating graphene oxide into TiO2 with 5%, 10% and 15%,
respectively. The results obviously demonstrate the signicant
inuence of graphene oxide on the optical characteristics in which
increasing graphene oxide amount narrows the band gap of TiO2,
the phenomena could be ascribed to the formation of TiAOAC
chemical bonding in the prepared composites [39].
Table 1 shows the BET surface area of TiO2 nanospindle and
TiO2/RGO. Comparing with TiO2, there are signicant increase in
the BET area of TiO2/RGO, indicating that the physical adsorptivity
of the composite is clearly improved.
The photoluminescence (PL) properties of the TiO2 nanostruc-
tures can give useful information about the separation and recom-
bination characteristics of the photoexcited electronhole pairs.
Fig. 7 shows the PL emission spectra of TiO2 nanospindle and the
TiO2/RGO composites. By this technique, the differences originat-
ing from the different optical absorption of the samples can be
eliminated [40,41]. It can be found that the spectra of TiO2/RGO
samples appear to be similar with TiO2 nanospindle, which means
that RGO has not induced new photoluminescence. In addition, the
PL intensity of TiO2/RGO is weakened than Pure TiO2, and with the
increasing amount of GO, the reduction is signicantly obvious.
This signicant reduction in the emission measurement veries
the good electron transfer capability of the TiO2/RGO nanocompos-
ite due to the excellent electron transportation properties of
graphene.
Fig. 8 shows photodegradation of MB curves by P25, TiO2
nanospindle and TiO2/RGO as catalysts. We compared the photo-
catalytic activity of the as-synthesized nanospindles with commer-
cial P25 under identical conditions. The activity of the anatase TiO2
nanospindles is apparently higher than that of P25, and this may be
due to the exposure of more {0 0 1} facets on the former [42]. The
adsorption equilibrium concentration of MB of TiO2/RGO(15%)
after 50 min was 0.78 mg/L, which were lower than that of TiO2
nanospindle, TiO2/RGO(5%) and TiO2/RGO(10%). The time of whole
 H. Wu et al. / Journal of Alloys and Compounds 623 (2015) 298303 301

(a) (b)

100nm

(c) (d) (e)

graphene
TiO 2

Fig. 5. (a) SEM image, (b) TEM image, (c and d) HRTEM image of the TiO2 nanospindle and (e) TEM image of TiO2/RGO(5%).

Fig. 6. UVVis diffuse reectance spectra of (a) TiO2 nanospindle, (b) TiO2/RGO(5%), Fig. 7. photoluminescence emission spectra of (a) TiO2 nanospindle, (b) TiO2/
(c) TiO2/RGO(10%) and (d) TiO2/RGO(15%). RGO(5%), (c) TiO2/RGO(10%) and (d) TiO2/RGO(15%).

Table 1
photocatalytic activity can also be attributed to the signicantly
The BET surface area of TiO2 nanospindle and TiO2/GR.
enhanced electronhole pairs (EHPs) separation with the electron
TiO2 nanospindle TiO2/GR(5%) TiO2/GR(10%) TiO2/GR(15%) injection into graphene which effectively hinder the photogenerat-
BET/m g2 1
59 82.3 89.7 97.6 ed EHPs recombination, and the remaining hole in TiO2. Will expo-
sure at surface state to oxidize MB [43]. It is also the reason that
why the photocatalytic activity of TiO2/RGO(15%) is better than
others. Cycling use as well as maintaining high activity of
MB was degraded as Fig. 9 shows. The results indicated the photocatalysts is a critical issue toward long-term photocatalytic
benecial role of graphene oxide in methylene blue photodegrada- applications. So we added MB to the equilibrium solution to repeat
tion, which due to the enhanced physical adsorptivity of graphene the photodegradation experiment as Fig. 10 shows. We found that
oxide, that the BET specic area of TiO2/RGO(15%) was 97.6 m2/g the degradation efciency of TiO2/RGO(15%) almost remain
which were larger than TiO2 nanospindle, TiO2/RGO(5%) and unchanged, suggesting the performance of TiO2/RGO(15%) was
TiO2/RGO(10%) as we mentioned earlier. Besides, enhanced great.
302 H. Wu et al. / Journal of Alloys and Compounds 623 (2015) 298303
Fig. 8. The time of whole MB was degraded under UVVis over P25, TiO2
nanospindle and TiO2/RGO.
Fig. 9. Remaining MB in solution: (a) initial and equilibrated with P25, TiO2
nanospindle and TiO2/RGO.
Fig. 10. Cycling tests of photocatalytic activity of the TiO2/RGO(15%) for MB
degradation.
4. Conclusion
In summary, crystalline anatase TiO2 nanospindles were syn-
thesized successfully which {0 0 1} facets are preferentially
exposed. Then the hydrothermal method was employed to synthe-
size TiO2/RGO hybrid nanostructures, this method produced a
TiO2RGO hybrid with strong interactions between the two com-
ponents, and the photocatalytic activity for degradation of MB is
much higher than that of pure TiO2 nanospindle under identical
conditions. The enhancement is caused by the excellent electron
conductivity and increased adsorptivity of RGO. Cycling use of
the as-synthesized sample indicates that the stability is high.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Nos. 21306150, 21176199 and 51372201),
the Specialized Research Fund for the Doctoral Program of Higher
Education of China (No. 20136101110009), the Shaanxi Provincial
Research Foundation for Basic Research, China (No. 2013JQ2003),
the Scientic Research Foundation of Education Department of
Shaanxi Provincial Government, China (No. 2013JK0693), the
Scientic Research Foundation of Northwest University (No.
12NW19), and the Scientic Research Staring Foundation of
Northwest University (No. PR12216).
References
[1] M.A. Fox, M.T. Dulay, Chem. Rev. 93 (1993) 341357.
[2] M. Inagaki, Y. Nakazawa, M. Hirano, Y. Kobayashi, M. Toyoda, Int. J. Inorg.
Mater. 3 (2001) 809811.
[3] M.R. Hoffmann, S.T. Martin, W. Choi, Chem. Rev. 95 (1995) 6996.
[4] Q.J. Xiang, J.G. Yu, M. Jaroniec, Nanoscale 3 (2011) 36703678.
[5] J.A. Byrne, P.A. Fernandez-Ibanez, P. Dunlop, D. Alrousan, J. Hamilton, Int. J.
Photoenergy 2011 (2011) 112.
[6] H.G. Yang, G. Liu, S.Z. Qiao, C.H. Sun, Y.G. Jin, S.C. Smith, J. Am. Chem. Soc. 131
(2009) 40784083.
[7] L. Pan, J.J. Zou, S.B. Wang, X.Y. Liu, X.W. Zhang, L. Wang, ACS. Appl. Mater
Interfaces 4 (2012) 16501655.
[8] X.H. Yang, Z. Li, G. Liu, J. Xing, C.H. Sun, H.G. Yang, Cryst. Eng. Commun. 13
(2011) 13781383.
[9] J.S. Chen, Y.L. Tan, C.M. Li, Y.L. Cheah, D.Y. Luan, S. Madhavi, J. Am. Chem. Soc.
132 (2010) 61246130.
[10] M.L. Zhao, L.P. Li, H.F. Lin, L.S. Yang, G.S. Li, Chem. Commun. 49 (2013) 7046
7048.
[11] P.F. Fu, P.Y. Zhang, Appl. Catal. B 96 (2010) 176184.
[12] C.M. Wang, Y. Zhang, V. Shutthanandan, S. Thevuthasan, G. Duscher, J. Appl.
Phys. 95 (2004) 50605068.
[13] Z.Y. Zhong, Y.D. Yin, B. Gates, Y.N. Xia, Adv. Mater. 12 (2000) 206209.
[14] V. Subramanian, E. Wolf, P. Kamat, J. Phys. Chem. B 105 (2001) 1143911446.
[15] O. Akhavan, M. Abdolahad, Y. Abdi, S. Mohajerzadeh, Carbon 47 (2009) 3280
3287.
[16] X.Y. Zhang, H.P. Li, X.L. Cui, Y. Lin, J. Mater. Chem. 20 (2010) 28012806.
[17] N. Zhang, Y. Zhang, Y.J. Xu, Nanoscale 4 (2012) 57925813.
[18] F. Schedin, A.K. Geim, S.V. Morozov, E.M. Hill, P. Blake, M.I. Katsnelson, K.S.
Novoselov, Nat. Mater. 6 (2007) 652655.
[19] T. Takamura, K. Endo, L. Fu, Y.P. Wu, K.J. Lee, T. Matsumoto, Electrochim. Acta
53 (2007) 10551061.
[20] S. Watcharotone, D.A. Dikin, S. Stankovich, R. Piner, I. Jung, G.H.B. Mommett, G.
Evmenenko, S.E. Wu, S.F. Chen, C.P. Liu, Nano Lett. 7 (2007) 18881892.
[21] N. Zhang, Y. Zhang, X. Pan, M.Q. Yang, Y.J. Xu, J. Phys. Chem. C 116 (2012)
1802318031.
[22] Y.Y. Liang, H.L. Wang, H.S. Casalongue, Z. Chen, H.J. Dai, Nano Res. 3 (2010)
701705.
[23] O. Akhavan, M. Abdolahad, A. Esfandiar, M. Mohatashamifar, J. Phys. Chem. C
114 (2010) 1295512959.
[24] W. Fan, Q. Lai, Q. Zhang, Y. Wang, J. Phys. Chem. C 115 (2011) 1069410701.
[25] W.S. Hummers, R.E. Offeman, J. Am. Chem. Soc. 80 (1958). 13391339.
[26] Y.X. Xu, H. Bai, G.W. Li, G.Q. Shi, J. Am. Chem. Soc. 130 (2008) 58565857.
[27] M. Choucair, P. Thordarson, J.A. Stride, Nat. Nanotechnol. 4 (2009) 3033.
[28] J. Jiang, F. Gu, X. Ren, Y.H. Wang, W. Shao, C.Z. Li, G.J. Huang, Ind. Eng. Chem.
Res. 50 (2011) 90039008.
[29] M.A. Pimenta, G. Dresselhaus, M.S. Dresselhaus, L.G. Cancado, A. Jorio, R. Saito,
Phys. Chem. Chem. Phys. 9 (2007) 12761290.
[30] W. Zhang, J. Cui, C. Tao, Y. Wu, Z. Li, L. Ma, Y. Wen, G. Li, Angew. Chem. Int. Ed.
48 (2009) 58645868.
[31] I. Calizo, A.A. Balandin, W. Bao, F. Miao, C.N. Lau, Nano Lett. 7 (2007) 2645
2649.
[32] O. Akhavan, E. Ghaderi, Small 9 (2013) 35933601.
[33] C. Nethravathi, M. Rajamathi, Carbon 46 (2008) 19941998.
[34] J.S. Park, S.M. Cho, W.J. Kim, J. Park, P.J. Yoo, ACS Appl. Mater. Interfaces 3
(2011) 360368.
[35] G. Williams, B. Seger, P.V. Kamat, ACS Nano 2 (2008) 14871491.
[36] O. Akhavan, E. Ghaderi, J. Phys. Chem. C 113 (2009) 2021420220.
 H. Wu et al. / Journal of Alloys and Compounds 623 (2015) 298303 303

[37] L.C. Chen, Y.C. Ho, W.S. Guo, C.M. Huang, T.C. Pan, Electrochim. Acta 54 (2009)
38843891.
[38] H. Zhang, X. Lv, Y. Li, Y. Wang, J. Li, ACS Nano 4 (2010) 380386.
[39] Y.J. Xu, Y. Zhuang, X. Fu, J. Phys. Chem. C 114 (2010) 26692676.
[40] O. Akhavan, E. Ghaderi, Nanoscale 5 (2013) 1031610326.
[41] O. Akhavan, E. Ghaderi, J. Mater. Chem. B 1 (2013) 62916301.
[42] L. Song, Y. Zhang, X. Wu, Z.G. Liang, Q.F. Yue, F.Y. Q, X. Zhang, Mater. Lett. 100
(2013) 198200.
[43] X. Pan, Y. Zhao, S. Liu, Carol.L. Korzeniewski, S. Wang, Z.Y. Fan, ACS Appl. Mater.
Interfaces 4 (2012) 39443950.