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www.rsc.org/pccp PAPER
Synthesis of gold@carbon dots composite nanoparticles for surface
enhanced Raman scatteringw
Peihui Luo, Chun Li and Gaoquan Shi*
Received 10th March 2012, Accepted 2nd April 2012
Published on 02 April 2012. Downloaded by RMIT Uni on 05/06/2013 07:24:01.

DOI: 10.1039/c2cp40767a

Gold@carbon dots composite nanoparticles (Au@CDs) with ultrathin carbon dot (CD) shells of
ca. 2 nm were prepared by reducing HAuCl4 with CDs at 100 1C. By adjusting the feeding mass
ratio of HAuCl4 to CDs, the average diameters of Au@CDs can be modulated from 8 to 44 nm.
The suspension of Au@CDs with an average diameter of ca. 24 nm was applied as a substrate for
surface enhanced Raman scattering (SERS) and it exhibited a higher SERS effect for rhodamine
6G (Rh6G) than the suspension of pure Au nanoparticles with nearly the same size. The excellent
SERS effect of Au@CDs is mainly attributed to their improved capability of adsorbing the
aromatic probe molecules.

1 Introduction dyes.9,20,30–32 However, the current interest in CDs is still

Carbon dots (CDs) are a new type of quantum dots,1 and have
attracted a great deal of attention in recent years because of
their promising applications in bioimaging,2–5 optoelectronic
devices,6,7 pollutant detection8 and catalysis.9,10 In comparison with
conventional inorganic quantum dots, CDs have many advantages
including low-toxicity, chemical inertness, biocompatibility and no
photo-bleaching. In addition, typical CDs contain a large amount
of hydrophilic carboxyl and hydroxyl groups, imparting them
with excellent water solubility and multifunctions. Since the
first report on the photoluminescence (PL) of the carbon
nanoparticles separated from single-walled carbon nanotubes,11
various methods have been explored for preparing CDs,
including arc-discharge,11 laser-ablation,2,12–14 electrochemical
oxidation,6,15–18 combustion,19–23 microwave assisted techni-
ques,24,25 etc.5,26–29 Among them, electrochemical oxidation is
one of the most widely used methods. This technique is
convenient, cheap and environmentally friendly, avoiding high
temperatures and hazardous chemical reagents. As-prepared
CDs were usually used directly without further modifications.
Recently, several nanocomposites based on CDs were reported
and they showed organic photovoltaic properties, photocatalytic
activities for CO2 conversion, or the degradation of organic
Department of Chemistry, Tsinghua University, Beijing 100084,
People’s Republic of China. E-mail: gshi@tsinghua.edu.cn;
Fax: +86 106 277 1149; Tel: +86 106 277 3743
w Electronic supplementary information (ESI) available: Quantum
yield measurements, cyclic voltammograms of an electrochemical
process, FTIR of CDs, SAED pattern and cross-sectional composi-
tional line profiles of Au@CDs, UV-visible absorption spectra and
TEM images of Au@CDs synthesized under different conditions,
TEM image of pure Au nanoparticles, SERS spectra of RhB. See
DOI: 10.1039/c2cp40767a
mainly focused on their synthesis and inherent properties.
Surface enhanced Raman scattering (SERS) has become a
powerful spectroscopic technique for structural characterizations
and sensing.33–35 SERS substrates are usually the coinage metals
such as Ag, Au, Cu with roughened surfaces or in the form of
nanoparticles. The signal enhancement of SERS is believed to be
originated from electromagnetic enhancement caused by surface
plasmon resonance (SPR) of metallic substrates, and a chemical
enhancement involving the interactions between metallic substrates
and adsorbed target molecules.36 The SPR can be simply tuned by
changing the sizes, shapes or aggregates of metallic nanoparticles.
In order to improve the chemical enhancement, it is necessary
to modify the surfaces of metallic nanoparticles with functional
groups to enhance the adsorption of analytes. Recently, Tian
et al. exploited a new SERS operation mode, called shell-isolated
nanoparticle-enhanced Raman spectroscopy (SHINERS).37 The
Raman signal amplification is performed by using Au nano-
particles with silica or alumina shells. The essential requirements
of these shells are that they should be ultrathin (1–2 nm),
chemically inert and pinhole-free. SHINERS can be applied
for sensing various samples with different contours or in a
complicated chemical environment (e.g. biological or electro-
chemical systems), avoiding the interferences caused by direct
contact of probe molecules or impurities with Au substrates.38
However, these chemically inert shells (e.g. silica, alumina) are
not beneficial for the adsorption of organic probe molecules
because of a lack of strong interactions.
In this paper, we report the synthesis of Au@carbon dots
(Au@CDs) with an ultrathin CDs shell of ca. 2 nm by
reducing HAuCl4 with CDs at 100 1C. This method is different
from those reported previously; no reductant20 or irradiation9
was applied for reducing the inorganic salts. Furthermore,
Au@CDs with different sizes can be conveniently obtained via

7360 Phys. Chem. Chem. Phys., 2012, 14, 7360–7366 This journal is c the Owner Societies 2012

adjusting the feeding mass ratio of CDs to HAuCl4 or chan-
ging the reaction temperature. The composite nanoparticles
have ultrathin CD shells, which are propitious to adsorb
aromatic molecules such as rhodamine 6G (Rh6G) for enhan-
cing their Raman signals. Actually, the Au@CDs exhibited a
SERS performance superior to that of pure Au nanoparticles
with nearly the same size.
2 Experimental
2.1 Materials
Chloroauric acid tetrahydrate (Au, 47.6%) and hydrogen
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peroxide (30%) were purchased from Sinopharm Chem. Reagent
Co., Ltd (Shanghai, China). Sodium citrate (99%), sulphuric acid
(98%), ethanol (99.7%) and acetone (99.5%) were bought from
Beijing Chem. Plant (Beijing, China). Dipotassium hydrogen
phosphate trihydrate (99%) and potassium dihydrogen phosphate
(99.5%) were obtained from Xilong Chem. Industry Co., Ltd
(Shantou, China). Quinine hemisulfate monohydrate (99%) was
bought from Alfa Aesar. Graphite rods were purchased from
Beijing Jixingsheng’an Industry and Trade Co., Ltd (Beijing,
China). Rhodamine 6G (95%) was purchased from Aldrich.
Rhodamine B (95%) was bought from Beijing Yinfeng Science
and Technol. Co., Ltd (Beijing, China). All the chemicals were
used as received.
2.2 Preparation of CDs
CDs were electrochemically synthesized according to the
method reported previously with a few modifications,17 and the
details are described as follows. The electrochemical preparation
was performed in a one-compartment electrochemical cell using a
CHI 440 potentiostat under computer control. Both the working
and the counter electrodes were graphite rods (10 cm  + 0.5 cm)
for improving the output of CDs, and a saturated calomel
electrode (SCE) was used as the reference electrode. The electrolyte
was a 0.1 M phosphate buffer solution (PBS, pH = 6.99). The
CDs were prepared by repeated potential scanning in the range of
3.0 V to 3.0 V at a scan rate of 0.1 V s1. During the process, the
colour of the electrolyte solution changed from colourless to
yellow and finally to dark brown. After 200 cycles of potential
scanning, the electrolyte solution was purified by filtrating it
through a filter membrane (cellulose ester membrane, pore
size = 220 nm) and successively dialyzed in water with a
cellulose ester membrane bag (1000 molar mass cutoff) for
over 4 days. After these treatments, the resulting solution was
ultrafiltered with a 10 000 molar mass cutoff membrane. A
light yellow carbon dots solution was obtained by collecting
the liquid passing through the cutoff membrane.
2.3 Synthesis of Au@CDs
The procedure for preparing the typical Au@CDs with an
average diameter of ca. 24 nm is as follows. 150 mL aqueous
solution of HAuCl4 (0.83 mg mL1) was added to 3 mL
aqueous suspension of CDs (0.03 mg mL1). The mixed
solution was kept at 100 1C for 80 min to yield a stable purple
suspension of Au@CDs. The monodisperse suspensions of
Au@CDs with different sizes can be obtained via the same
procedure by adjusting the feeding mass ratio of CDs to HAuCl4
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or reaction temperature. For example, under identical reaction
conditions except for decreasing the reaction temperature
from 100 to 60 1C, Au@CDs with a broader size distribution
and larger average diameter were obtained.
2.4 Synthesis of Au nanoparticles
According to Frens’ method,39 25 mL of HAuCl4 (0.01% by
weight) was heated to boiling; then, 375 mL aqueous solution
of sodium citrate (1% by weight) was added. After reaction for
30 min, a wine red suspension of Au nanoparticles was
obtained and the average diameter of the nanoparticles was
measured to be ca. 29 nm.
2.5 Characterization
X-ray photoelectron spectra (XPS) were recorded on an
ESCALAB 250 photoelectron spectrometer (ThermoFisher
Scientific) with Al Ka (1486.6 eV) as the X-ray source set at
150 W and a pass energy of 30 eV for high resolution scan.
UV-visible spectra were recorded on a U-3010 UV-visible
spectrometer (Hitachi, Japan). Fluorescence spectra were measured
by using a LS 55 fluorescence spectrometer (PerkinElmer). Fourier
transform infrared spectroscopy (FTIR) was carried out on a
Spectrum GX FTIR system (PerkinElmer). Transmission electron
microscope (TEM) images were acquired with a HITACHI
H-7650B TEM at 80 kV. High-resolution transmission electron
microscope (HRTEM) images, selected area electron diffraction
(SAED) pattern, scanning transmission electron microscopy
(STEM) image, elemental analysis mapping and cross-sectional
compositional line profiles were taken by using a Tecnai G2 F20
S-Twin HRTEM operated at 200 kV. The samples were prepared
by depositing the Au@CDs on a carbon nanotube (CNT) grid.40
An atomic force microscopic (AFM) image was taken using a
Nanoscope III MultiMode SPM (Digital Instruments) with an
AS-12 (‘‘E’’) scanner operated in tapping mode in conjunction
with a V-shaped tapping tip (Applied Nanostructures SPM
model: ACTA). The Au concentrations in nanoparticle
suspensions were measured using a VISTA-MPX inductively
coupled plasma-atomic emission spectrometer (ICP-AES,
VARIN, USA). Raman and SERS spectra were recorded on
a RM 2000 Microscopic confocal Raman spectrometer
(Renishaw PLC, England) with a 633 nm He–Ne laser beam.
The spot diameter of the laser beam was about 5 mm. The
accumulation time for obtaining each spectrum was 30 s. The
liquid samples for SERS measurements were prepared by
adding the aqueous solution of probe molecules to the suspension
of Au@CDs or Au nanoparticles. Successively, the obtained
mixtures were sonicated for 30 min to accelerate the absorption
of probe molecules on the particle surfaces. The solid samples
for SERS measurements were prepared through the following
procedures. First, silicon wafer was cleaned by sequential
ultrasonication in acetone, ethanol, de-ionized water for 10 min
in each medium and then treated with H2SO4 (98%)/H2O2 (30%)
(3 : 1, v/v) at room temperature for 4 h to generate a hydrophilic
surface. After repeated rinsing with Milli-Q ultrapure water,
the clean silicon wafer was dried by blowing nitrogen gas.
Then, 50 mL Au@CDs or pure Au nanoparticle suspensions
(0.044 mg mL1) were drop-cast onto the silicon substrate.
After evaporation of water at 60 1C, 10 mL of 0.42 mM
Phys. Chem. Chem. Phys., 2012, 14, 7360–7366 7361

aqueous solution of Rh6G was dropped onto the above
substrate and dried in air.
3 Results and discussion
3.1 Morphologies
The electrochemical preparation of CDs was performed in 0.1 M
PBS by using graphite rods as both the working and counter
electrodes (Fig. S1 and S2, ESIw). The diameters of CDs were
measured to be 2.1  0.4 nm (Fig. 1a–c). The HRTEM image
(Fig. 1a, inset) clearly reveals a lattice spacing of 0.207 nm and
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this value is in agreement with that of the (101) facet of graphite.
Therefore, the obtained CDs have a graphitic structure.
Fig. 2a shows the typical TEM images of Au@CDs synthesized
via heating the mixture of 3 mL of CDs (0.03 mg mL1) and
150 mL of HAuCl4 (1 mg mL1) at 100 1C for 80 min. The
Au@CDs are nearly spherical in shape with diameters of
24  3 nm. Each composite nanoparticle has a low-contrast halo
ring associated with a continuous CD layer wrapping around a
high-contrast Au core, revealing the formation of a core–shell
structure. The selected area electron diffraction (SAED) pattern
(Fig. S3, ESIw) of Au@CDs displays the diffraction rings assigned
to face-centred cubic (fcc) Au (111), (200), (220) and (311) planes,
respectively. The HRTEM images of single (Fig. 2b), double
(Fig. 2c) and several (Fig. 2d) Au@CDs on a CNT grid also
Fig. 1 (a, b) TEM images of CDs with different magnifications; inset of (a): HRTEM image of single CD. (c) Size distribution of CDs.
Fig. 2 (a) TEM image of Au@CDs on a carbon film coated copper grid; inset: size distribution of Au@CDs. (b–d) HRTEM images of Au@CDs
on a CNT grid. (e) STEM image, (f) Au or (g) C element mapping of single Au@CDs shown in (b) or (e).
7362 Phys. Chem. Chem. Phys., 2012, 14, 7360–7366
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clearly demonstrate that the Au cores are coated by ultrathin shells
of ca. 2 nm thickness. This value is equivalent to the average
diameter of CDs. Elemental mapping distributions of a single
composite nanoparticle (Fig. 2e) indicate that both Au and C
elements cover the whole nanoparticle (Fig. 2f and g). The cross-
sectional compositional line profiles of the composite nanoparticle
also reflect that the Au@CDs have a core–shell structure (Fig. S4,
ESIw). Au@CDs with average diameters smaller than 24 nm can be
obtained by decreasing the amount of HAuCl4 in the reaction
mixture (Fig. S5, ESIw). Au@CDs can also be synthesized at a
lower temperature (e.g. 60 1C). Unfortunately, their size distribution
was broadened and their optical absorption was red-shifted, com-
pared with the counterparts prepared at 100 1C (Fig. S6–S8, ESIw).
3.2 Optical properties
The UV-visible spectrum of a CD aqueous dispersion does not
show any peaks and its absorbance decreases with the increase
in wavelength (Fig. 3a). The aqueous dispersion of CDs also
exhibits typical excitation-dependent PL behaviour (Fig. 3b).6
The most intense PL of the CD dispersion appears at 445 nm
upon excitation at 330 nm. The aqueous solution of CDs is
yellowish under daylight and it emits strong blue luminescence
when excited by a 365 nm UV light (Fig. 3a, inset). On the
other hand, the UV-visible spectrum of an Au@CD aqueous
dispersion has a typical plasmon absorption peak associated
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Fig. 3 (a) UV-visible absorption spectrum of CDs aqueous suspension (0.03 mg mL1); inset: a photograph of CDs aqueous suspension excited by
daylight (left) or a 365 nm UV lamp (right). (b) PL spectra of CDs aqueous dispersion (0.03 mg mL1) upon excitation at the indicated wavelengths.

Fig. 4 (a) UV-visible absorption spectrum of Au@CDs aqueous suspension. (b) PL spectrum of CDs or Au@CDs aqueous suspension excited at 330 nm.

with their Au cores at 543 nm (Fig. 4a). The formation of
Au@CDs partly quenched the PL of CDs as shown in Fig. 4b.
Actually, the quantum yield of Au@CDs aqueous suspension
was measured to be 0.5% upon excitation at 330 nm, and this
value is much lower than that of the CDs suspension (2%)
measured under the same conditions (Fig. S9, ESIw). This
phenomenon can be explained by the photoinduced electron
transfer from CD shells to Au cores and the aggregation
of CDs.
3.3 Structural characterization
C 1s X-ray photoelectron spectra (XPS) of CDs or Au@CDs
are illustrated in Fig. 5a or b. The peaks at 284.7, 285.7, 287.8
and 288.8 eV are assigned to C–C, C–OH, CQO, and
OQC–OH groups, respectively.3,18,41 According to this figure,
the oxygenated groups of CDs were partly removed after forming
the core–shell composite nanoparticles. Actually, the C–O atomic
ratio of Au@CDs was measured to be 2.2, and this value is
higher than that of CDs (1.8). Heating pure HAuCl4 solution
under the same conditions did not produce any Au nano-
particles. Therefore, it is reasonable to conclude that the
formation of Au nanoparticles is ascribed to the redox reaction
between CDs and AuCl4 ions, which is similar to the reaction
between HAuCl4 and graphene oxide.41 In this case, CDs acted as
a reducing agent and part of their oxygenated groups were further
oxidized and removed from the reaction system upon heating.
Furthermore, the CD layers coated on Au nanoparticles also
acted as a capping agent, the residual oxygenated groups of the
CD coating made the core–shell nanoparticles dispersible in
water. Raman spectra of CDs and Au@CDs are shown in
Fig. 5c. The spectrum of CDs does not show any Raman signal
under our measurement conditions because of its strong
fluorescence background. However, the Raman spectrum of
Au@CDs exhibits typical bands of carbon nanocrystals at ca.
1357 cm1 (D band) and 1587 cm1 (G band). These spectral
observations also imply that the strong fluorescence of CDs in
Au@CDs was partly quenched via the photoinduced electron
transfer from CD shells to Au cores, indicating that CDs were
firmly coated on Au nanoparticles.

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Fig. 5 (a, b) C 1s XPS and (c) Raman spectra of CDs and Au@CDs.

3.4 SERS properties of probe molecules that produce a SERS signal ISERS. On the
basis of the Rh6G Raman band at 1360 cm1, the EF of
To investigate the SERS activity of the Au@CDs, Rh6G was
Au@CDs and Au nanoparticle suspensions was calculated to
used as the probe molecule because of its well-established
be 8.8  103 and 2.0  103, respectively. The EF of gold
Raman features and large Raman scattering cross section.42,43
nanoparticle suspension is comparable to that reported in the
The SERS comparison of Au@CDs and pure Au nano-
literature.46,47 These results indicate that the CD shells of
particles was conducted in aqueous media for obtaining
Au@CDs greatly improved the EF of Au nanoparticles by
reproducible and comparable spectra. Fig. 6a displays the
about 4 times in aqueous dispersions. The SERS spectra of
SERS spectra of 0.38 mM Rh6G in the aqueous dispersion
Au@CDs with different concentrations of Rh6G did not show
of Au@CDs (diameter = ca. 24 nm, Fig. 2a) or Au nano-
significant changes in their overall features (Fig. 6b). However,
particles (diameter = ca. 29 nm, Fig. S10, ESIw) with the same
the Raman intensity increased with the increase in the concen-
concentration of nanoparticles (in terms of Au content). The
tration of probe molecules. This phenomenon is attributed to
prominent bands in the range of 1000–1650 cm1 are assigned
the increased amounts of Rh6G adsorbed on the surfaces of
to either xanthene or phenyl ring stretching modes.44 The
Au@CDs. The limit of detection was tested to be about 38 nM
spectrum of Rh6G at Au@CDs has fine features with high
(signal to noise ratio Z 3), indicating that the as-fabricated
signal to noise ratios. However, the SERS signals at Au
Au@CDs substrate can be used to detect the aromatic dye
nanoparticles are too weak to provide any useful information.
molecules with high sensitivity.
The enhancement factors (EF) were calculated by using the
The improved SERS performance of Au@CDs can be
following equation:45
explained as follows. First, the CDs in the peripheries of
ISERS CRaman Au@CDs were negatively charged because of the ionization of
EF ¼  their residual carboxyl groups (Fig. S2, ESIw, and Fig. 5b), and they
IRaman CSERS
also have a conjugated graphitic structure (the inset of Fig. 1a).
where CRaman is the concentration of probe molecules that Therefore, the CD shells of Au@CDs make them capture
produce a Raman signal IRaman, and CSERS is the concentration more positively charged Rh6G molecules than Au nanoparticles

Fig. 6 (a) SERS spectrum of 0.38 mM Rh6G in Au@CDs or Au nanoparticles suspension with the same nanoparticle concentration of
0.044 mg mL1, and Raman spectrum of 4.2 mM Rh6G aqueous solution. (b) SERS spectra of Rh6G with different concentrations in a
0.044 mg mL1 Au@CDs suspension.

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Fig. 7 UV-visible spectra of a 7.6 mM Rh6G solution, and the
remaining solution of 7.6 mM Rh6G after the adsorption by
0.44 mg mL1 Au@CDs or Au nanoparticles.
Fig. 8 SERS spectra of 0.42 mM Rh6G drop-cast on solid Au@CDs/
Si and Au/Si substrates.
via p–p stacking and electrostatic interactions. As shown in
Fig. 7, the UV-visible absorbance of a 7.6 mM Rh6G solution
after the adsorption by 0.44 mg mL1 Au nanoparticles is much
higher than that of the solution after the adsorption by the same
amount of Au@CDs. According to this figure, in this case, the
amount of Rh6G adsorbed by Au@CDs is about 5 times that
adsorbed by Au nanoparticles. The SERS spectrum of a 42 nM
Rh6G solution drop-cast on the solid substrate of Au@CDs/Si
or Au/Si is shown in Fig. 8. The Au@CDs/Si substrate also
showed a SERS performance superior to that of the Au/Si
substrate. This phenomenon is attributed to the additional
chemical enhancement of Au@CDs. Rhodamine B (RhB)
was also used as the probe molecule to evaluate the SERS
effect of Au@CDs. It was found that RhB exhibited similar
behavior to Rh6G in SERS measurements, possibly because it
has a structure similar to that of Rh6G (Fig. S11, ESIw).
4 Conclusions
Au@CDs with ultrathin CD shells of ca. 2 nm have been
successfully prepared by directly reducing HAuCl4 with CDs
at 100 1C. Au@CDs can be applied as SERS substrates for
detecting aromatic dye molecules and exhibited SERS performance
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superior to that of pure Au nanoparticles. The excellent SERS
effect of Au@CDs was mainly caused by absorbing more aromatic
dye molecules via p–p stacking and electrostatic interaction. The
Au@CDs also showed stronger chemical enhancement because of
their enhanced interaction with the probe molecules. Considering
that CDs have a special affinity for aromatic molecules, they will
have potential applications in SERS detection of aromatic mole-
cules closely associated with our daily life, such as toxic melamine
or explosive nitroaromatic compounds.
Acknowledgements
This work is supported by National Basic Research Program
of China (973 Program, 2012CB933402), Natural Science
Foundation of China (91027028, 51161120361) and Open
Research Fund of State Key Laboratory of Bioelectronics
(Southeast University, China).
Notes and references
1 S. N. Baker and G. A. Baker, Angew. Chem., Int. Ed., 2010, 49,
6726–6744.
2 L. Cao, X. Wang, M. J. Meziani, F. Lu, H. Wang, P. G. Luo,
Y. Lin, B. A. Harruff, L. M. Veca, D. Murray, S.-Y. Xie and
Y.-P. Sun, J. Am. Chem. Soc., 2007, 129, 11318–11319.
3 S. C. Ray, A. Saha, N. R. Jana and R. Sarkar, J. Phys. Chem. C,
2009, 113, 18546–18551.
4 R. Liu, D. Wu, S. Liu, K. Koynov, W. Knoll and Q. Li, Angew.
Chem., Int. Ed., 2009, 48, 4598–4601.
5 S. Zhu, J. Zhang, C. Qiao, S. Tang, Y. Li, W. Yuan, B. Li, L. Tian,
F. Liu, R. Hu, H. Gao, H. Wei, H. Zhang, H. Sun and B. Yang,
Chem. Commun., 2011, 47, 6858–6860.
6 Y. Li, Y. Hu, Y. Zhao, G. Shi, L. Deng, Y. Hou and L. Qu, Adv.
Mater., 2011, 23, 776–780.
7 F. Wang, Y. Chen, C. Liu and D. Ma, Chem. Commun., 2011, 47,
3502–3504.
8 H. X. Zhao, L. Q. Liu, Z. D. Liu, Y. Wang, X. J. Zhao and
C. Z. Huang, Chem. Commun., 2011, 47, 2604–2606.
9 L. Cao, S. Sahu, P. Anikumar, C. E. Bunker, J. Xu, K. A. Shiral
Fernando, P. Wang, E. A. Guliants, K. N. Tackett, II and
Y.-P. Sun, J. Am. Chem. Soc., 2011, 133, 4754–4757.
10 H. Li, X. He, Z. Kang, H. Huang, Y. Liu, J. Liu, S. Lian, C. H.
A. Tsang, X. Yang and S.-T. Lee, Angew. Chem., Int. Ed., 2010, 49,
4430–4434.
11 X. Xu, R. Ray, Y. Gu, H. J. Ploehn, L. Gearheart, K. Raker and
W. A. Scrivens, J. Am. Chem. Soc., 2004, 126, 12736–12737.
12 Y.-P. Sun, B. Zhou, Y. Lin, W. Wang, K. A. Shiral Fernando,
P. Pathak, M. J. Meziani, B. A. Harruff, X. Wang, H. Wang,
P. G. Luo, H. Yang, M. E. Kose, B. Chen, L. Monica Veca and
S.-Y. Xie, J. Am. Chem. Soc., 2006, 128, 7756–7757.
13 S.-L. Hu, K.-Y. Niu, J. Sun, J. Yang, N.-Q. Zhao and X.-W. Du,
J. Mater. Chem., 2009, 19, 484–488.
14 X. Li, H. Wang, Y. Shimizu, A. Pyatenko, K. Kawaguchi and
N. Koshizaki, Chem. Commun., 2011, 47, 932–934.
15 J. Zhou, C. Booker, R. Li, X. Zhou, T.-K. Sham, X. Sun and Z. Ding,
J. Am. Chem. Soc., 2007, 129, 744–745.
16 Q.-L. Zhao, Z.-L. Zhang, B.-H. Huang, J. Peng, M. Zhang and
D.-W. Pang, Chem. Commun., 2008, 5116–5118.
17 L. Zheng, Y. Chi, Y. Dong, J. Lin and B. Wang, J. Am. Chem.
Soc., 2009, 131, 4564–4565.
18 J. Lu, J. Yang, J. Wang, A. Lim, S. Wang and K. P. Loh, ACS
Nano, 2009, 3, 2367–2375.
19 H. Liu, T. Ye and C. Mao, Angew. Chem., Int. Ed., 2007, 46, 6473–6475.
20 L. Tian, D. Ghosh, W. Chen, S. Pradhan, X. Chang and S. Chen,
Chem. Mater., 2009, 21, 2803–2809.
21 A. B. Bourlinos, A. Stassinopoulos, D. Anglos, R. Zboril,
M. Karakassides and E. P. Giannelis, Small, 2008, 4, 455–458.
22 F. Wang, S. Pang, L. Wang, Q. Li, M. Kreiter and C. Liu, Chem.
Mater., 2010, 22, 4528–4530.
Phys. Chem. Chem. Phys., 2012, 14, 7360–7366 7365

23 D. Pan, J. Zhang, Z. Li, C. Wu, X. Yan and M. Wu, Chem.
Commun., 2010, 46, 3681–3683.
24 H. Zhu, X. Wang, Y. Li, Z. Wang, F. Yang and X. Yang, Chem.
Commun., 2009, 5118–5120.
25 X. Wang, K. Qu, B. Xu, J. Ren and X. Qu, J. Mater. Chem., 2011,
21, 2445–2450.
26 H. Peng and J. Travas-Sejdic, Chem. Mater., 2009, 21, 5563–5565.
27 D. Pan, J. Zhang, Z. Li and M. Wu, Adv. Mater., 2010, 22, 734–738.
28 B. Zhang, C. Liu and Y. Liu, Eur. J. Inorg. Chem., 2010, 4411–4414.
29 J. Lu, P. S. E. Yeo, C. K. Gan, P. Wu and K. P. Loh, Nat.
Nanotechnol., 2011, 6, 247–252.
30 Y.-P. Sun, X. Wang, F. Lu, L. Cao, M. J. Meziani, P. G. Luo, L. Gu
and L. Monica Veca, J. Phys. Chem. C, 2008, 112, 18295–18298.
31 J. Li, B. Zhang, F. Wang and C. Liu, New J. Chem., 2011, 35,
554–557.
32 V. Gupta, N. Chaudhary, R. Srivastava, G. D. Sharma, R. Bhardwaj
Published on 02 April 2012. Downloaded by RMIT Uni on 05/06/2013 07:24:01.
and S. Chand, J. Am. Chem. Soc., 2011, 133, 9960–9963.
33 S. Nie and S. R. Emory, Science, 1997, 275, 1102–1106.
34 J. P. Camden, J. A. Dieringer, J. Zhao and R. P. Van Duyne, Acc.
Chem. Res., 2008, 41, 1653–1661.
35 Z.-Q. Tian, B. Ren, J.-F. Li and Z.-L. Yang, Chem. Commun.,
2007, (34), 3514–3534.
36 H. Ko, S. Singamaneni and V. V. Tsukruk, Small, 2008, 4, 1576–1599.
7366 Phys. Chem. Chem. Phys., 2012, 14, 7360–7366
View Article Online
37 J. F. Li, Y. F. Huang, Y. Ding, Z. L. Yang, S. B. Li, X. S. Zhou,
F. R. Fan, W. Zhang, Z. Y. Zhou, D. Y. Wu, B. Ren, Z. L. Wang
and Z. Q. Tian, Nature, 2010, 464, 392–395.
38 J.-F. Li, S.-B. Li, J. R. Anema, Z.-L. Yang, Y.-F. Huang, Y. Ding,
Y.-F. Wu, X.-S. Zhou, D.-Y. Wu, B. Ren, Z.-L. Wang and
Z.-Q. Tian, Appl. Spectrosc., 2011, 65, 620–626.
39 G. Frens, Nature (London), Phys. Sci., 1973, 241, 20–22.
40 L. Zhang, C. Feng, Z. Chen, L. Liu, K. Jiang, Q. Li and S. Fan,
Nano Lett., 2008, 8, 2564–2569.
41 N. Zhang, H. Qiu, Y. Liu, W. Wang, Y. Li, X. Wang and J. Gao,
J. Mater. Chem., 2011, 21, 11080–11083.
42 J. Guthmuller and B. Champagne, ChemPhysChem, 2008, 9,
1667–1669.
43 K. Kneipp, H. Kneipp, I. Itzkan, R. R. Dasari and M. S. Feld,
Chem. Rev., 1999, 99, 2957–2975.
44 E.-O. Ganbold, J.-H. Park, U. Dembereldorj, K.-S. Ock and
S.-W. Joo, J. Raman Spectrosc., 2011, 42, 1614–1619.
45 E. C. Le Ru, E. Blackie, M. Meyer and P. G. Etchegoin, J. Phys.
Chem. C, 2007, 111, 13794–13803.
46 M. Roca and A. J. Haes, J. Am. Chem. Soc., 2008, 130,
14273–14279.
47 J. Huang, Y. Sun, S. Huang, K. Yu, Q. Zhao, F. Peng, H. Yu,
H. Wang and J. Yang, J. Mater. Chem., 2011, 21, 17930–17937.
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