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Acta Materialia 64 (2014) 326332
www.elsevier.com/locate/actamat

Green synthesis of dimension-controlled silver

nanoparticlegraphene oxide with in situ ultrasonication
K.S. Hui a,, K.N. Hui b,, D.A. Dinh b, C.H. Tsang c, Y.R. Cho b, Wei Zhou d,
Xiaoting Hong e, Ho-Hwan Chun f
b

a
Department of Mechanical Engineering, Hanyang University, 17 Haengdang-dong, Seongdong-gu, Seoul 133-791, Republic of Korea
School of Materials Science and Engineering, Pusan National University, San 30 Jangjeon-dong, Geumjeong-gu, Busan 609-735, Republic of Korea
c
Department of System Engineering and Engineering Management, City University of Hong Kong, Hong Kong, PR China
d
Department of Mechanical & Electrical Engineering, Xiamen University, Xiamen 361005, China
e
School of Chemistry & Environment, South China Normal University, Key Laboratory of Theoretical Chemistry of Environment,
Ministry of Education, Guangzhou 510006, China
f
Global Core Research Center for Ships and Oshore Plants (GCRC-SOP), Pusan National University, San 30 Jangjeon-dong,
Geumjeong-gu, Busan 609-735, Republic of Korea

Received 20 May 2013; received in revised form 19 October 2013; accepted 23 October 2013
Available online 20 November 2013

Abstract
A green chemical approach to control the dimensions of Ag nanoparticle-decorated graphene oxide (AgNPGO) composites was proposed by in situ ultrasonication of a mixture of AgNO3 and GO solution with the assistance of vitamin C acting as an environmentally
friendly reducing agent at room temperature. The AgNPGO composites were characterized by X-ray diraction, transmission electron
microscopy, energy-dispersive spectroscopy, Fourier transform infrared spectroscopy, Raman spectra and ultravioletvisible absorption
spectra. The results demonstrated that Ag nanoparticles with an average diameter of 15 nm were uniformly dispersed on the surface of
GO nanosheets by in situ ultrasonication of 1 min with vitamin C. Increasing the ultrasonication times resulted in Ag nanoparticles with
tunable dimensions ranging from 15 to 55 nm being formed on the surface of GO nanosheets. The amount of silver nitrate and the ultrasonication time play a key role in the control of the dimension of Ag nanoparticles on GO, and a formation mechanism of the asprepared AgNPGO composites is proposed. This study provides a guide to controlling the dimensions of AgNPGO composites, which
may hold promise as advanced materials for various analytical applications such as catalysis, sensors and microchips.
2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Keywords: Silver nanoparticles; Graphene oxide; Ultrasonication; Vitamin C

1. Introduction
For a decade, the development of graphene has received
considerable attention because it possesses unique properties, such as a two-dimensional extended honeycomb network of sp2 hybridized carbon atoms [13], high electron
mobility (200,000 cm2 V1 s1) [4], a large theoretical
Corresponding authors. Tel.: +82 2 2220 0441; fax: +82 2 2220 2299
(K.S. Hui), tel.: +82 051 510 2467; fax: +82 051 514 4457 (K.N. Hui).
E-mail addresses: kshui@hanyang.ac.kr (K.S. Hui), bizhui@pusan.
ac.kr (K.N. Hui).

specic surface area (2630 m2 g1) [5], excellent mechanical, chemical and thermal properties [6] and high electrical
conductivity (103104 S m1) [7]. Based on these unique
properties, graphene has become a promising advanced
building material for potential applications in many technological elds, including nanoelectronics [8,9], nanocomposites [10,11], energy storage devices [12,13], transparent
electrodes for displays [14,15] and solar cells [16,17]. Yet
the superb properties of graphene have been signicantly
improved by exploiting the hybridization of graphene,
which is an important step in the development of

1359-6454/$36.00 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.actamat.2013.10.045

K.S. Hui et al. / Acta Materialia 64 (2014) 326332

multifunctional materials with synergistic properties [18

27]. In particular, noble metal nanoparticles (Au, Pt, Pd,
etc.) on graphene composites have attracted tremendous
interest because of the novel optical, electronic, mechanical
and catalytic properties of the resulting materials [2831].
Therefore, their fabrication has become a topic of scientic
and technological importance. In addition, the dispersion
of metal nanoparticles on graphene sheets potentially provides a new way to develop catalytic [32,33], magnetic
[34,35] and optoelectronic materials [36,37]. Among them,
Ag nanoparticle (AgNP)-decorated graphene has been
demonstrated to be the most promising material for optoelectronics [38,39], catalysis [40,41] and electrochemistry
[42]. However, challenges in the fabrication of metal nanoparticle/graphene composites remain. For example, the use
of surfactant or stabilizing agent molecules, which are
introduced and strongly absorbed on the surface of metal
nanoparticles, result in a discrepancy in the performance
of metal nanoparticle/graphene composites [4345]. In
addition, AgNPgraphene composites are usually obtained
from the in situ reduction of silver precursors with hazardous reducing agents such as sodium borohydride, formaldehyde and hydrazine on the preformed graphene or
decoration graphene with pre-fabricated AgNPs, which
involves multi-steps and requires complex manipulation
[18,46,47]. Accordingly, the syntheses of metal nanoparticlegraphene oxide (GO) nanocomposites employing GO
as a starting precursor has been attracting a great deal of
attention. This is because GO consists of oxidized graphene
sheets that have their basal planes mostly decorated with
hydroxyl, epoxide, carbonyl and carboxyl groups [48],
which allows AgNPs to interact with the GO sheets
through physisorption, electrostatic binding or through
charge-transfer interactions [49]. In particular, carboxylic
moieties on a GO surface can stabilize the silver cations
that can directly attach to the carboxyl groups. Thus, the
reduction takes place on the surface of the exfoliated
sheets, giving one-step formation of Ag nanoparticles
attached to the exfoliated GO sheets without the need for
functionalization [18]. Fernandez-Merino et al. [50] have
investigated the deoxygenation eciency of GO suspensions by vitamin C at 95 C and concluded that vitamin
C can compete in terms of reducing ability with the widely
employed, but highly toxic, reducing agent hydrazine used
for graphene synthesis. Thus far, the eorts have been
focused on the eective performance of the metal nanoparticleGO or graphene composites [3842]. However, few
studies have comprehensively investigated the eects of
synthesis parameters on controlling the dimension and
morphology of metal nanoparticleGO composites. To
resolve this gap, we propose a fast, green, low-cost, largescale and environmentally friendly preparation of dimension-controlled Ag nanoparticle-decorated graphene oxide
(AgNPGO) composites at room temperature. Herein,
the AgNPGO was prepared by in situ ultrasonication
at room temperature with the assistance of vitamin C
(ascorbic acid), a natural antioxidant essential for many

327

metabolic functions in living organisms [51], which acts

as a nontoxic reducing agent. The AgNPGO composites
were characterized by X-ray diraction (XRD), transmission electron microscopy (TEM), energy-dispersive spectroscopy, Fourier transform infrared (FT-IR) spectroscopy,
Raman spectra and ultravioletvisible (UVvis) absorption
spectra. The possible formation mechanism of the dimension-controlled AgNPGO is proposed. Composites were
prepared at various concentrations of silver precursors
(AgNO3) under dierent ultrasonication times in order to
explore the inuence of ultrasonic waves on the dimension
and morphology of the AgNPGO composites.
2. Experimental
2.1. Materials
Graphite powders were obtained from Unichem Chemical Reagent Co. Ltd. (South Korea). AgNO3, NaNO3 and
vitamin C were provided by Guangdong Guanghua SciTech Co. Ltd. (China). All the other chemicals and
reagents were of analytical grade and purchased from
SigmaAldrich unless otherwise stated. All solutions were
prepared using ultrapure water (Millipore, 18.2 MO cm).
A Buehler sonic cleaner (UltraMet 2005) was used for the
ultrasound source. The ultrasonic frequency used was
20 kHz 50 Hz.
2.2. Synthesis of AgNPGO composites

Graphite oxides were prepared by a modied Hummers

procedure as previously reported [52,53] and exfoliated
into GO nanosheets by ultrasonication for 1 h. AgNP
GO composites were prepared by mixing AgNO3 aqueous
solution at various concentrations of 0.1, 0.2 and 0.6 M, and
50 ml of GO suspensions (0.4 mg ml1) under a sonication
bath for 30 min. Afterwards, vitamin C (5 mM) was added
slowly to the reaction mixture under continuous ultrasonication for another 30 min. The suspension was then
washed with deionized water three times and dried at
60 C for 12 h to obtain the as-prepared AgNPGO composites. In addition, in order to investigate the eect of
an ultrasonic wave on the morphology of the AgNPGO
composites, composite samples with 0.1 M AgNO3 were
prepared with an analogous experimental process, but the
ultrasonication time was adjusted for 1, 5, 10, 20 and
30 min, respectively. Table 1 summarizes the sample information at various experimental conditions, corresponding
to the names of the samples.
2.3. Characterization
The morphology and nanostructure of the prepared
samples were observed using Philips Tecnai 12 BioTWIN
TEM operated at 120.0 kV. The TEM samples were prepared under ambient conditions by depositing droplets of
the aqueous suspensions onto carbon lms supported by

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K.S. Hui et al. / Acta Materialia 64 (2014) 326332

Table 1
Summary of the synthesis conditions and the corresponding sizes of the
Ag nanoparticles on GO.
Sample Sample
no.
name

1
2
3
4
5
6
7

AgNPs-GO
AgNPs-GO
AgNPs-GO
AgNPs-GO
AgNPs-GO
AgNPs-GO
AgNPs-GO

Experiment conditions

Ag
particle
AgNO3 GO Vitamin Ultrasonic
size
(mol/l) (mg) C
time (min)
(nm)
(mmol/l)
0.630
0.230
0.130
0.120
0.110
0.15
0.11

0.6
0.2
0.1
0.1
0.1
0.1
0.1

20
20
20
20
20
20
20

5
5
5
5
5
5
5

30
30
30
20
10
5
1

20120
13100
4555
1750
35
2025
15

copper grids. The Raman spectra were obtained on a

Dongwoo Optron (Model: Vector-01FX) confocal Raman
spectrometer with an argon-ion (488 nm) laser source. All
FT-IR spectra were recorded using a ZnSe prism in a Tensor 27 spectrometer (Bruker, Germany). The angle of incidence of the IR radiation was 45 in a wave number range
of 40001000 cm1, and 200 scans were obtained and averaged with a resolution of 4 cm1. The absorption spectrum
of the samples was examined in a wavelength range of 200
800 nm, using a UVvis spectrophotometer (HP 8453,
Agilent).
3. Results and discussion
The preliminary investigations of the formation of the
Ag nanoparticles on the composite samples were carried
out by XRD analysis. In Fig. 1, the signicant peak at
10.14 and the weak diraction peak at 22.5 indicate the
removal of surface oxy-functional groups and the restacking of reduced GO sheets during the drying process of GO
[54]. The XRD patterns of the Ag nanoparticles on the GO
sheets using dierent concentrations of aqueous AgNO3
solution are shown in Fig. 1bd. The prominent peaks at
38.1, 44.3, 64.5 and 77.5 were assigned to the (1 1 1),
(2 0 0), (2 2 0) and (3 1 1) crystallographic planes of the face
centered cubic (fcc) Ag nanoparticles, respectively (JCPDS
card No. 07-0783). The broad diraction peaks of GO at
10.14 and 22.5 are disappeared in AgNPGO sheets, indicating that the combination of vitamin C and in situ ultrasonication can completely exfoliate GO and expand the
restacked GO. Noticeably, the high-intensity diraction
peak observed at 38.1 of the composite sample with
0.6 M AgNO3, indicating the crystalline Ag, conrms that
the nanoparticles are composed of the crystalline Ag. The
XRD pattern demonstrated that AgNPs had been successfully incorporated with GO and they worked as spacers to
prevent the restacking of the GO sheets [55].
The eect of the concentration of AgNO3 solution on
the shape and size of AgNP composites was further investigated by TEM. Fig. 2 shows the representative TEM
images of the AgNPGO composites at dierent concentrations of AgNO3, which was reported in Table 1. The
TEM data show that the wide distribution of the size and

Fig. 1. XRD patterns of (a) GO, and the synthesized Ag nanoparticles on

GO using dierent concentration of the AgNO3 solution: (b) 0.1 M, (c)
0.2 M and (d) 0.6 M.

morphology of Ag nanoparticles can be obtained on GO

sheets by changing AgNO3 concentration with in situ ultrasonication at room temperature (Fig. 2ac). The composite
with AgNO3 concentration at 0.6 M reveals the size of the
nanoparticles ranging in diameter from 10 to 120 nm, and
nanoparticles consist of dierent shapes such as rod, spherical, triangle, pentagonal and ellipsoid (Fig. 2a). Therein,
the smaller particle is spherical in shape, whereas the bigger
particles were recorded as an elongated form. This elongated shape was attributed to an agglomeration of the
Ag nanoparticles at high concentration. Specically, the
size of Ag nanoparticles decreases with decreasing AgNO3
concentration, and the Ag particles tended to be sphericallike at lower AgNO3 concentration (Fig. 2b and c). A
similar study reported that the morphology of the Ag
nanoparticles gradually changes from an agglomerated formation to a uniformly distributed formation when the
AgNO3 concentration decreases [55]. The formation mechanism of AgNPGO composites can be understood as the
functional groups (hydroxyl, epoxide, carbonyl and carboxylic groups) uniformly existing on the basal plane and
edges of the GO. These functional groups provide multiple
binding sites for Ag ions to form an Ag+GO complex by
electrostatic interaction between Ag+ cations and negatively charged GO [56]. Subsequently, Ag+ and GO were
in situ gradually reduced by vitamin C to AgNPs on the
surface of GO. Results clearly provide evidence that the
size and shape of AgNPs can be controlled using vitamin
C with in situ ultrasonication assistance at room temperature, which may have potential for many technological synthesis processes that require low temperature. Fig. 2d
shows the TEM image of the GO sheets with wrinkles
and folds. The crystallinity of Ag nanoparticles was further
investigated by high-resolution TEM and selected-area
electron diraction (SAED). Fig. 2e shows the HRTEM
image of Ag nanoparticle embedded on the GO sheets
(Sample 2). The measured fringe lattice of Ag nanoparticle
is found to be 0.236 nm, which corresponds to the (1 1 1)

K.S. Hui et al. / Acta Materialia 64 (2014) 326332

329

Fig. 2. TEM images of the Ag nanoparticles on the GO sheets: (a) Ag nanoparticles synthesized at 0.6 M AgNO3, (b) Ag nanoparticles synthesized at
0.2 M AgNO3, (c) Ag nanoparticles synthesized at 0.1 M AgNO3, (d) TEM images of the GO sheets, (e) HRTEM image of Ag nanoparticles
synthesized at 0.2 M AgNO3 and (f) SAED image of the Ag nanoparticles synthesized at 0.2 M AgNO3.

crystal plane. Fig. 2f shows the SAED patterns of synthesized Ag nanoparticles with concentration of AgNO3 as
0.2 M (Sample 2). The diraction dots are well resolved
in the SAED image, providing strong evidence to support
the single crystallinity of these nanoparticles.
To study the eect of the ultrasonication on the dimension and morphology of AgNPGO composites, the structural characteristics of the AgNPGO composite with a
0.1 M AgNO3 concentration and a particle size of 45
55 nm (Fig. 2c) were further examined at various times of
ultrasonication. TEM images (Fig. 3) revealed the morphology of the AgNPGO composite with 0.1 M AgNO3
at various ultrasonication times. The corresponding particle size of the AgNPs attached on GO was also reported
in Table 1. High-magnication TEM images revealed that
the composite samples possessed a uniform morphological
distribution of AgNPs at 1, 5 and 10 min of ultrasonication, whereas the composite samples at 20 and 30 min of
ultrasonication performed a formation with big and small
Ag particles. In general, the particle size increase corresponds to the increases in the ultrasonication time. The

mechanism of this phenomenon can be understood by Ostwald ripening [5759]. Accordingly, there are big and small
Ag particles that coexist on the GO sheet. The atoms on
the surface of these Ag particles are less stable than those
on the inside. The vibration eect and the thermal generation from the ultrasonic process then drives the surface
atoms on the small particles, which tend to detach from
the particles and diuse into the solution. Long duration
ultrasonication increases the concentration of the free molecules in solution. When these free molecules are supersaturated, they have a tendency to condense on the lager
particles. Therefore, all the smaller particles shrink, while
the larger particles grow, and the overall average size
increases (Table 1). The formation of AgNPs in Fig. 3ae
also conrms that the increase in particle size during long
duration ultrasonication (30 min) results in the agglomeration of AgNPs, which depresses the uniform distribution of
the AgNPs on GO sheets.
UVvis spectroscopy was used to monitor the formation
of GO and AgNPGO with 0.1 M AgNO3 composites and
to show the presence of Ag nanoparticles using vitamin C.

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K.S. Hui et al. / Acta Materialia 64 (2014) 326332

Fig. 3. TEM images of the AgNPGO composite at dierent times of ultrasonication: (a) 30 min, (b) 20 min, (c) 10 min, (d) 5 min and (e) 1 min.

In Fig. 4, the two characteristic peaks observed in the UV

vis spectrum of GO are a signal at 231 nm, which ascribes
the p ! p transitions of the aromatic CAC bonds, and a
shoulder at 300 nm, which is derived from the n ! p transitions of the C@O bonds [39,60]. In contrast, the characteristic peak of 231 nm of the AgNPGO composite
samples was broadened compared to those of the GO sample. This broadening suggests the charge transfer interactions between the GO and the Ag nanoparticles [61]. The
formation of the Ag nanoparticles was indicated by the surface plasmon resonance peak of the Ag nanoparticles at
around 431 nm in the AgNPGO samples [46,6264]. It
was reported that the charge-transfer complexes between
Ag nanoparticles and GO lead to the absorption of light
at excitation frequency to produce a chemical surfaceenhanced Raman scattering (SERS) eect [65], and the
degree of chemical SERS eect depends on particle size,

Fig. 4. UV-vis absorption spectra of GO and AgNPGO composite with

0.1 M AgNO3 at ultrasonication time: (a) 1 min, 5 min, (c) 10 min, (d)
20 min and (e) 30 min.

shape, chemical surrounding and adsorbed species on the

surface [55]. It is noted that the intensity of the surface
plasmon peak at 431 nm increases with decreasing dimension of Ag nanoparticles (Table 1). This is attributed to
the increases in contact area between Ag nanoparticles
and GO in the composites when the sizes of Ag nanoparticles decrease. Thus, the increase in contact area causes the
increase of charge-transfer complexes, and thus enhances
the chemical SERS eect.
To further conrm the reduction ability of vitamin C,
the FI-IR spectra of the composite samples were examined.
Fig. 5 shows the FI-IR spectra of GO and AgNPGO with
0.1 M AgNO3 composites (Sample 3). In the spectrum of
GO, the typical absorption peaks are listed as follows:
the strongest band at 3385 cm1 and 1220 cm1 correspond
to the OAH stretching vibrations of COAH in carboxylic
acids and phenolic groups: two peaks at 1725 cm1 and
1614 cm1 assigned to the asymmetric and symmetric
stretch vibration of the carboxyl groups mas(COO) and ms
(COO), respectively. As for the AgNPGO (Sample 3),
the peak positions of the functional groups on GO still
remained, and their shape was similar. In particular, the
intensity of the mas(COO) stretching vibration decreased,
whereas that of the ms(COO) stretching vibration increased.
This reverse change proves that the interaction between the
AgNPs and the oxygen-containing functional groups (i.e.,
ACOOH) of the GO nanosheets by forming a chemical
bond or simple electrostatic attraction was consistent with
a similar previous report [66].
Raman spectroscopy is also one of the most sensitive
and informative techniques to characterize disorder sp2
carbon material. The representative Raman spectra of
GO and AgNPGO (Sample 3) are shown in Fig. 6. The
typical feature for AgNPGO in the Raman spectra are a
D band around 1351 cm1 and a G band around

K.S. Hui et al. / Acta Materialia 64 (2014) 326332

Fig. 5. FT-IR spectrum of (a) GO and (b) AgNPGO composite with

0.1 M Ag at ultrasonication of 30 min.

331

a nontoxic reducing agent. Most signicantly, vitamin C

was reconrmed to be a substitute for other toxic reducing
agents in the reduction of metal ion precursors. The results
of the characterization demonstrate that Ag NPs were uniformly dispersed on the surface of the GO nanosheets, and
dimensions of Ag NPs ranging from 15 to 120 nm could be
obtained by controlling the concentration of silver precursor solution and the ultrasonication time. Furthermore, the
formation mechanism of the AgNPGO nanocomposites is
proposed as follows: Ag+ may bind with the negatively
charged oxygen-containing functional group on the surface
of GO via an electrostatic force and may also adsorb on the
surface of GO by virtue of an Ag+p orbital interaction.
Subsequently, uniform distribution of Ag NPs on GO composites was reduced by employing vitamin C with in situ
ultrasonication assistance at room temperature. The eect
of ultrasonication on the dimension and morphology of
the AgNPGO composites with 0.1 M AgNO3 concentration was further examined. Results show that the Ag NP
size increased and dispersed uniformly on the GO sheets
with the increase in the ultrasonication time. This could
be explained by the Ostwald ripening phenomenon. Based
on the results, a new prospective green synthesis route in
controlling the morphology of the metallic particles in
GO composites with ultrasonication assistance was
obtained. We therefore expect that this green method for
the preparation and synthesis of AgNPGO hybrids will
lead to further development of a broad new class of
metalGO hybrids with enhanced properties for many
technological applications.
Acknowledgements

Fig. 6. Raman spectrum of GO and AgNPGO composite with 0.1 M Ag

at ultrasonication of 30 min, showing that the presence of AgNPs on GO
enhances the intensity of the D and G bands.

1602 cm1. Therein, the D band was assigned to the

breathing mode of the j-point phonons of A1g symmetry,
which represents the disorder or defects in carbon atoms
created by the attachment of hydroxyl and epoxide groups
on the carbon basal plane [67], while the G band introduces
the E2g phonon of the carbon sp2 atoms. The ratio of the
intensities of the D and the G bands (ID/IG) were calculated. The ID/IG ratio of the AgNPGO was 0.865, which
is similar to that of GO (0.854). The intensity of these
bands for AgNPGO lm increased 680% in comparison
to the GO lm, indicating the SERS activity [68]. The
SERS enhancement in AgNPGO is ascribed to the formation of charge-transfer complexes through chemical interaction, such as physisorption between Ag nanoparticles
and GO [69].
4. Conclusions
In summary, we developed a green method at room temperature to prepare AgNPGO nanocomposites with
in situ ultrasonication assistance, employing vitamin C as

This work was supported by the research fund of

Hanyang University (HY-2013 year). This work was supported by Basic Science Research Program through the
National Research Foundation of Korea (NRF) funded
by the Ministry of Education, Science and Technology
(2013R1A1A2007365), the Korea Foundation for the
Advancement of Science & Creativity (KOFAC), and
funded by the Korean Government (MOE), and the National Research Foundation of Korea (NRF) grant funded
by the Korea government (MSIP) through GCRC-SOP
(No. 2011-0030013).
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