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Cite this: New J. Chem., 2012, 36, 97–101

www.rsc.org/njc PAPER
One-pot hydrothermal synthesis of graphene quantum dots
surface-passivated by polyethylene glycol and their photoelectric
conversion under near-infrared lightw
Jianhua Shen, Yihua Zhu,* Xiaoling Yang, Jie Zong, Jianmei Zhang and
Published on 25 October 2011 on http://pubs.rsc.org | doi:10.1039/C1NJ20658C

Chunzhong Li
Received (in Victoria, Australia) 29th July 2011, Accepted 11th October 2011
DOI: 10.1039/c1nj20658c

A novel and simple approach for preparing graphene quantum dots surface-passivated by
polyethylene glycol (GQDs-PEG) has been developed by a one-pot hydrothermal reaction, using
small graphene oxide (GO) sheets and polyethylene glycol (PEG) as starting materials.
The prepared GQDs-PEG show excellent luminescence properties, the PL quantum yield of the
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GQDs-PEG with 360 nm emission was about 28.0%, which was two times higher than the pure
GQDs. Interestingly, the GQDs-PEG possess the upconversion photoluminescence (UCPL)
properties. Blue PL was clearly shown both under the ultraviolet and 808 nm laser in the
fluorescent microscopy images. So the GQDs-PEG may provide a new type of fluorescence and
upconversion material for applications in bioscience and energy technology. Especially, the
GQDs-PEG showed higher photocurrent generation capability. And their photoelectrode generated an
obvious and stable photocurrent under a 808 nm near-infrared (NIR) laser. Due to the low cost and
simple method, GQDs-PEG thus provide a cost-effective dopant material for solar energy conversion.

1. Introduction
Graphene, a single layer of carbon atoms in a honeycomb
structure, has generated enormous excitement due to its large
surface area, high carrier transport mobility, superior mechanical
flexibility and excellent thermal/chemical stability.1 The size-
dependent bandgap of graphenes was particularly interesting
for photovoltaic applications. With bulk graphene having a
zero bandgap, in principle the bandgap of graphenes can be
tuned from 0 eV to that of benzene by varying their sizes.2,3
Interestingly, they also possess upconversion photoluminescence
(PL) properties. Graphenes with these unique properties could
be an efficient platform for the photoelectrochemical (PEC) cells.
To facilitate the application of graphene in nanodevices and
effectively tune the bandgap of graphenes, a promising approach
is to convert the 2D graphene sheets into 0D graphene quantum
dots (GQDs). However, these GQDs exhibited a new pheno-
menon due to the quantum confinement and edge effects.
And GQDs are similar to carbon quantum dots (CQDs).
Key Laboratory for Ultrafine Materials of Ministry of Education,
School of Materials Science and Engineering, East China University
of Science and Technology, Shanghai 200237, China.
E-mail: yhzhu@ecust.edu.cn, czli@ecust.edu.cn;
Fax: +86 21 6425 0624; Tel: +86 21 6425 2022
w Electronic supplementary information (ESI) available: Representation
of the samples and quantum yield measurements. See DOI: 10.1039/
c1nj20658c
Over the past few decades, CQDs are attracting considerable
attention as nascent quantum dots, as they may gradually
replace traditional semiconductor quantum dots due to their
superiority in chemical inertness, biocompatibility and low
toxicity.4–8 However, the disadvantage is that CQDs possess
size effects, and quasispherical nanoparticles with sizes below
10 nm.4 Therefore, the GQDs and their chemical derivatives
have received more attention, as their diameters are mainly
distributed in a larger range (3–20 nm).9–16 In addition, Dai
and co-workers9 described intrinsic luminescence from single
layer nanographene oxide (NGO) sheets surface-passivated
by polyethylene glycol (PEG) in both the visible and NIR
regions. Kikkawa and colleagues10 reported a hydrazine
vapor reduction of graphene oxide (GO) into the GQDs with
broadband visible PL possessing a long NIR emission. Gokus
et al.11 discovered the induction of pronounced PL within
single-layer graphene flakes treated with an oxygen/argon
plasma. Qu et al.12 reported an electrochemical approach for
direct preparation of functional GQDs with a uniform size of
3–5 nm. Li et al.13,14 demonstrated a solubilization strategy for
GQDs, which proved to be attractive for efficient light harvesting
in photovoltaics. But these complex processes are difficult for
mass production. Pan et al.15 developed a simple hydrothermal
route for cutting preoxidized micrometre-sized rippled graphene
sheets into ultrafine graphene quantum dots (GQDs). However,
the produced GQDs emit strongly under alkaline conditions
whereas they are almost completely quenched in acidic media.

This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012 New J. Chem., 2012, 36, 97–101 97

Very recently, our group reported a method to prepare GQDs
surface-passivated by polyethylene glycol (GQDs-PEG) by
hydrazine hydrate reduction of GO.16
Here we present a simple and novel method to prepare
GQDs-PEG by a one-pot hydrothermal reaction, using small
GO sheets and PEG as starting materials. GO sheets were
reduced to GQDs and the hydroxyl groups ( OH) of PEG
were connected to the carboxyl groups ( COOH) of GQDs
simultaneously.9,15,17 For comparison, we also prepared
GQDs without the surface-passivation agent (similar to that
reported by Pan et al.; Fig. S1a in ESIw).15 Strong blue PL
was clearly shown both in the GQDs and GQDs-PEG under
365 nm. And the PL quantum yield of the GQDs-PEG with
Published on 25 October 2011 on http://pubs.rsc.org | doi:10.1039/C1NJ20658C
360 nm emission was about 28.0%, which was two times
higher than the GQDs (ca. 13.1%), comparable with those
of reported luminescent nanoparticles.18–21 Interestingly, the
upconverted PL properties of GQDs-PEG were much better
than those of GQDs, which were similar to the report.16 In
addition, Fig. S1b (ESIw) shows the pictures of the final large
aggregate products under sunlight and 365 nm UV lamp. Such
a novel and simple hybrid material with strong luminescence
would find significant applications in PEC cells. So we also
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demonstrated that GQDs-PEG had higher photon-to-electron
conversion capability compared with GQDs. Interestingly, the
GQDs-PEG photoelectrode generated an obvious and stable
photocurrent under a 808 nm near-infrared (NIR) laser.
2. Experimental
2.1. Reagents and materials
Graphite powder and PEG 10 000 were purchased from
Sinopharm Chemical Reagent Co., Ltd. And all other chemicals
were purchased from Shanghai Chemical Reagent Co. All
chemicals were used as received without any further purification.
Ultrapure water (18 MO cm 1) was used for all experiments.
2.2. Preparation of GQDs surface-passivated by PEG
GO was prepared from natural graphite powder by a modified
Hummers method.22,23 The sample GO (0.05 g) was treated
in an aqueous nitric acid solution (up to 2.6 M) (40 mL) with
70 1C reflux for 24 h. After cooling to room temperature, the
suspension was subjected to mild ultrasonication. The pH was
tuned to 7 with NaOH. The suspension was disrupted into
small pieces using an ultrasonic cell crusher for 60 min. The
sample was filtered through a 0.22 mm microporous membrane
to remove the large tracts of GO.
In a typical reaction, PEG 10 000 (0.2 g) was mixed with the
cutting GO solution (50 mL), and the mixture was substantially
mixed. The mixture solution was then transferred into a 100 mL
Teflon-lined stainless-steel autoclave and heated at 200 1C for
24 h. After cooling to room temperature, the resulting solution
was further dialyzed in a dialysis bag (retained molecular
weight: 14 000 Da) for a week and the GQDs-PEG showed
strong blue fluorescence. We also prepared the GQDs without
surface-passivation for the comparison.
2.3. Photocurrent response measurements
Commercial indium tin oxide (ITO) was used as the substrate
for electrode buildup, which was cleaned by sonication
98 New J. Chem., 2012, 36, 97–101 This journal is
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sequentially for 20 min each in acetone, 10% KOH in ethanol
and doubly deionized water. After the treatment, the solution
of GQDs-PEG and GQDs was spin-coated on the ITO. PEC
cells were measured in a three-electrode experimental system,
consisting of a QDs/ITO working electrode, a platinum wire
auxiliary electrode, and an Ag/AgCl (3 M KCl) reference
electrode. The electrolyte used in PEC cells was 0.1 M phos-
phate buffer solution (PBS) at pH = 6.8. A 365 nm UV lamp
(70 mW cm 2) was used as the light source. The photocurrent
signal was recorded with a CHI 660C workstation (CH
Instruments, Chenhua, Shanghai, China) connected to a personal
computer. All electrochemical experiments were carried out at
room temperature.
2.4. Characterizations
High-resolution TEM images were taken on a JEOL JEM
2011 microscope (JEOL, Japan) at an acceleration voltage of
200 kV. The specimen was prepared by drop casting the sample
dispersion onto a carbon-coated copper grid, followed by
drying under room temperature. PL spectra were measured on
a Fluorolog-3-P UV-VIS-NIR fluorescence spectrophotometer
(Jobin Yvon, France). The FT-IR spectrum was recorded on a
Nicolet 5700 Fourier transform infrared spectrometer and the
XRD spectrum of GQDs-PEG was investigated by X-ray
powder diffraction (RIGAK, D/MAX 2550 VB/PC, Japan).
The UV-vis spectrum of the GQDs dispersed in water was
obtained using a Unico UV-2102PC spectrophotometer.
Fluorescent microscopy images of GQDs-PEG were recorded
on a fluorescence inverse microscope (Nikon TE-2000 U). All
spectra were recorded with quartz cells of 10 mm path length.
3. Results and discussion
GQDs-PEG were prepared by a one-pot hydrothermal
reduction of GO sheets and PEG (Mw = 10 000). And then
the precursor removed excess PEG by a 14 000-molecular-weight
cutoff dialysis bag overnight. Fig. 1a shows the TEM image of
the as-prepared GQDs-PEG. The collected GQDs-PEG are
nearly monodispersed with a uniform diameter of ca. 5–25 nm
(13.0 nm average diameter, similar to the reported).15,16 The
absence of discernible lattice structures on the enlarged HRTEM
image (Fig. 1b) indicates that the resultant GQDs-PEG are
amorphous, which is further confirmed by the diffuse ring
pattern obtained by selected area electron diffraction (SAED;
inset in Fig. 1a). Fig. 1d–e show the fluorescent microscope
images of GQDs-PEG with the ultraviolet (UV) and 808 nm
NIR excitation lights from left to right, respectively. Blue PL is
clearly shown under the ultraviolet and the dark blue fluores-
cence is observed under a 808 nm NIR laser, which is consistent
with the PL spectra. The bright dots are the GQDs-PEG
aggregates, and the larger aggregates are also shown in the Fig.
S1 in ESI.w The X-ray diffraction pattern shows that the (002)
interlayer spacing is 3.81 Å (Fig. 2a) between the reduced
graphene sheets (3.68 Å) and the oxidized graphene sheets
(3.97 Å). The (002) interlayer spacing of GQDs-PEG is larger
than the reduced graphene sheets. Before the hydrothermal
treatment, the oxidized graphene sheets were oxidized in concen-
trated HNO3, and the (002) spacing increased to 3.97 Å. After
the hydrothermal treatment and the surface-passivation by PEG,
c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012

Fig. 1 (a) TEM image of the GQDs-PEG, the inset is the corres-
ponding selected area electron diffraction (SAED) pattern; (b) HRTEM
image of an individual GQD–PEG; (c) diameter distribution of the
Published on 25 October 2011 on http://pubs.rsc.org | doi:10.1039/C1NJ20658C
GQDs-PEG; (d, e) fluorescent microscopy images of GQDs-PEG under
the UV (330–400 nm) light and 808 nm NIR laser (scale bar: 100 mm).
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Fig. 2 (a) The XRD spectra of the grapheme, GQDs-PEG and GO.
(b) The FT-IR spectra of the GQDs-PEG and PEG.
the polymer chains were introduced at the edge and on the basal
plane. As shown in the Fourier transform infrared (FTIR)
spectrum (Fig. 2b), the peaks of PEG were shown in the
GQDs-PEG, and the peak at 1637 cm 1 is attributed to the
benzene ring vibration of CQC bonds. The broad peak centered
at 2888 cm 1 is assigned to the stretching vibrations of C–H
bonds, while the peak at 3434 cm 1 is attributed to the bending
vibrations of O–H bonds. In addition, the peak of O–H
(3434 cm 1) in the GQDs-PEG is higher than in the PEG, and
the hydrothermally treated GQDs are not completely reduced
and a lot of OH remained. The presence of these groups and
PEG makes the GQDs-PEG well soluble in water.
To further explore the optical properties of as-synthesized
GQDs-PEG, a detailed PL study was carried out using
different excitation wavelengths. Fig. 3a shows the normal
and normalized PL spectra of GQDs-PEG. The as-prepared
GQDs-PEG also exhibit an excitation-dependent PL behavior.
When the excitation wavelength was changed from 300 to
400 nm, the PL peaks shifted from 377 (black) to 493 nm (navy).
GQDs show the same phenomenon, but the PL peaks are
narrower and their intensity decreases rapidly, and the strongest
excitation wavelength has a blue shift from 340 nm to 320 nm
(Fig. 3b). Another marked difference involves the UV–vis
absorption of the GQDs-PEG and the GQDs dispersed in
water (Fig. 3c). For the GQDs, an absorption band at ca. 320 nm
is clearly observed, which is similar to that reported by Pan
et al.15 But the GQDs-PEG have no clear absorption peak but
a long absorption edge. And the threshold wavelength of
GQDs-PEG notably shifts from 343 to 323 nm when GQDs
were surface-passivated by PEG. The blue shift in threshold
wavelength indicates that the surface-passivation can increase
the energy gap of GQDs. The PL intensity of the GQDs-PEG
This journal is c The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2012
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Fig. 3 (a, b) PL emission spectra for the GQDs-PEG and GQDs at
different excitation wavelengths. Inset: the corresponding normalized
PL spectra. (c) UV–vis absorption and PL (at 360 nm excitation)
spectra of the GQDs-PEG and GQDs dispersed in water. Inset:
photographs of the GQDs-PEG and GQDs aqueous solutions taken
under visible light. (d) Upconverted PL spectrum of the GQDs-PEG
and GQDs excited at 808 nm.
is higher than the GQDs under the 365 nm excitation, and the
photographs also show the GQD-PEG aqueous solution has a
brighter blue fluorescence under 365 nm UV light. By selecting
rhodamine B in water as the standard and 360 nm as the
excitation wavelength, the PL quantum yield of the GQDs-PEG
was measured and calculated to be 28.0% (Table S1 in ESIw),
which was beyond two times higher than the GQDs (ca. 13.1%).
The value is higher than previously reported for GQDs.15 Due to
the surface-passivation agent, there must be a more quantum
confinement of emissive energy trapped to the GQDs surface,
namely, the GQDs with the surface-passivation exhibit stronger
PL.18 Both the GQDs-PEG and GQDs were shown to possess
the upconversion PL properties at the same concentration of the
solution. Fig. 3d shows the PL spectrum of GQDs-PEG excited
by 808 nm with the upconverted emissions located at about
464 nm, and its intensity over 10 times higher than the GQDs.
Remarkably, the GQDs-PEG are shown to possess stronger
UCPL properties, and we conducted further studies on
the upconversion performance. As shown in Fig. 4a, when
the excitation wavelength changed from 700 to 980 nm, the
upconverted emission peaks shifted from 431 to 544 nm,
respectively. And the shifting between the energy of upconverted
emission light (Em) and excitation light (Ex) was almost
unchanged, about 1.1 eV. Fig. 4b shows the linear relationship
between Em and Ex, and the function of the fit line is Em =
1.00Ex + dE (R2 = 0.9747) with dE = 1.1 eV. This result is
consistent with our previous report.16 We speculate on the
upconversion luminescence due to the anti-Stokes PL, where
the dE between the p and s orbitals is near 1.1 eV.16,24–27
These are very novel phenomena of optical properties in
GQDs-PEG, which are different from the report that the
upconverted PL property of CQDs should be attributed to
the multiphoton active process.6,28
Since the GQDs-PEG possessed strong luminescence and
peculiar upconversion PL, they would find significant applications
New J. Chem., 2012, 36, 97–101 99

Published on 25 October 2011 on http://pubs.rsc.org | doi:10.1039/C1NJ20658C
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Fig. 4 (a) Upconverted PL properties of the GQDs-PEG, inset is
the enlarged image of the PL spectrum excited at a 980 nm laser.
(b) The energy of the excitation light as a function of the emission, and
the function of the fit line is Em = 1.00Ex + dE (R2 = 0.9747) with
dE = 1.1 eV.
in PEC cells.29,30 So we also compared the photon-to-electron
conversion capability of the GQDs-PEG and GQDs. The
GQDs-PEG and GQDs were spin-coated on an ITO substrate.
Upon exposure to light, electron–hole pairs were generated
and disassociated in the GQDs-PEG, and then the electrons
were transported to ITO electrodes. Photocurrents generated
by GQDs-PEG and GQDs on ITO electrodes were measured
by the three-electrode system. As demonstrated in Fig. 5,
GQDs-PEG photoelectrode generated photocurrent with
higher density at 365 nm while the pure GQD photoelectrode
showed less than half of the photocurrent of the GQDs-PEG.
Fig. 5 Photocurrent response of the GQDs-PEG and GQDs photo-
electrodes under 365 nm UV light or 808 nm NIR laser.
100 New J. Chem., 2012, 36, 97–101 This journal is
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This result is consistent with their PL quantum yield. Meanwhile,
we also demonstrated the photoelectric conversion of the
GQDs-PEG under the 808 nm NIR laser. In contrast to the
ultraviolet, it shows a relatively small and stable photocurrent.
This means that GQDs-PEG will be a new solar cell dopant
material, the light of the photon-to-electron conversion may
be extended from the ultraviolet to the near infrared.
4. Conclusions
In summary, GQDs-PEG were prepared by a one-pot hydro-
thermal reaction and applied to construct the photoelectrode.
The GQDs-PEG photoelectrode generated a relatively small
photocurrent under a 808 nm NIR laser, and had higher
photon-to-electron conversion capability compared with the
pure GQDs. Compared with the GQDs, the GQDs-PEG
possessed higher fluorescence performance and upconversion
properties. GQDs-PEG may provide a new type of fluores-
cence and upconversion material for applications in bioscience
and energy technology. Especially, the GQDs-PEG showed
higher photocurrent generation capability. Due to the low cost
and simple method, GQDs-PEG thus provide a cost-effective
dopant material for solar energy conversion and other PEC
cells applications.
This work was supported by the National Natural Science
Foundation of China (20925621, 20976054 and 21176083), the
Innovation Program of Shanghai Municipal Education Com-
mission (09ZZ58), the Fundamental Research Funds for the
Central Universities, the Program for Changjiang Scholars
and Innovative Research Team in University (IRT0825), and
the Shanghai Leading Academic Discipline Project (project
number: B502) for financial supports.
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