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Optically Tunable Amino-Functionalized Graphene
Quantum Dots
Hiroyuki Tetsuka,* Ryoji Asahi, Akihiro Nagoya, Kazuo Okamoto, Ichiro Tajima,
Riichiro Ohta, and Atsuto Okamoto
Chemically-derived graphene quantum dots (GQDs) are
emerging as optical materials for prospective applications in
bio-imaging, light-emitting, and photovoltaic.[1–7] One of the
most notable issues is their potential for replacing commonly
used semiconductor nanocrystals including toxic/expensive
heavy-metals, in which the versatile tunability of optical prop-
erties, together with solution processability, has led to various
applications. However, because of the non-stoichiometric
nature of GQDs, tailor-made control of their optical proper-
ties is extremely challenging and is one of the key technologies
for putting these materials into practical use. Here, we report
optically tunable amino-functionalized graphene quantum dots
(af-GQDs) with discrete molecular weights and specific edges,
extracted through the ammonia-mediated bond-scission reac-
tion from oxidized graphene sheet. The af-GQDs exhibit clear
multiple colors under a single-wavelength UV excitation, and
their luminance quantum yields are over 40%. The optical prop-
erties are precisely controlled only by the quantitative function-
alization of af-GQDs, supported by MALDI-TOF mass analysis
and density functional theory calculations.
The primary approach to fabricate soluble fluorescent GQDs
was realized by either cutting graphene sheet through a con-
trolled oxidation or reduction process,[2,4,6,7] or constructing a
small precursor aromatic molecule to larger one followed by
oxidative exfoliation.[8] The presence of finite-sized molecular
sp2 domains and/or CO-related quasi-molecular fluorophores,
induced by adsorption of oxygen functional groups, could con-
fine π electrons and consequently give fluorescence to be dic-
tated by the nature of sp2 domains and functional groups.[9–11]
However, despite their different oxidation states and scales,
these GQDs exhibit similar blue fluorescence whose maximum
is centred at 420–450 nm, which is mainly ascribed to the
limited tunability of size and/or shape of sp2 domains and
adsorption of oxygen functional groups, arising from process
that focused only on insertion or removal of oxygen functional
groups. So far, the ideal tunable PL from GQDs has not yet
been successful, and it should be possible by enhancing the
homogeneity of local electronic modifications of graphene
through the precise control of sp2 domain size, edge structure,
and surface functionality of GQDs. In the view of remarkable
Dr. H. Tetsuka, Dr. R. Asahi, A. Nagoya, K. Okamoto,
I. Tajima, Dr. R. Ohta, A. Okamoto
Toyota Central R&D Laboratories Inc.,Nagakute
Aichi 480-1192, Japan
E-mail: h-tetsuka@mosk.tytlabs.co.jp
DOI: 10.1002/adma.201201930
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quantum-confinement and edge effect of quantum-sized
graphene, chemical doping is an effective way to tailor their
electronic characteristics. For instance, Li et al. demonstrated
that direct substitution with nitrogen (N) in the GQDs lattice
induces the modulation of the chemical and electronic charac-
teristics of the GQDs, because of high electronic affinity of the
N atom.[12] Although the N-doped GQDs exhibited a blue shift
in the PL emission from their N-free counterparts, such incor-
poration of heteroatoms in the graphene lattice would disrupt
sp2 hybridization of carbon (C) atoms, and tailor-made control
of optical properties is still lacking. Chemical modifications
using molecules with strong electron-donating or -accepting
ability, e.g., primary amines, could also drastically impact on
electronic characteristics of graphene,[13,14] thereby GQDs with
tunable properties must be realized through the selective and
quantitative functionalization of primary amines.
To tailor the optical properties, we have designed a novel
graphene nanostructure that is edge-terminated by a primary
amine, allowing the electronic structure to be modified system-
atically through the effective orbital resonance of amine moi-
eties with graphene core. Figure 1a presents our strategy for
the production of af-GQDs that starts from oxidized graphene
sheets (OGSs) (see Synthetic Methods in Supporting Infor-
mation for experimental details; Supporting Figure S1–S6).
We focused on a unique heterogeneous chemical struc-
ture of graphene oxide in which aromatic sp2 domains of
2–3 nm, which are surrounded by linearly aligned epoxy and/or
hydroxyl-bonded sp3 C atoms, are isolated within a continuous
sp3 C⫺O matrix. The graphitic sp2 domains in the pristine
OGSs we prepared were calculated to have a mean size of
∼2.7 nm according to the empirical Tuinstra–Koenig relation-
ship,[15] which is based on the Raman D/G peak-area ratio (Sup-
porting Figure S2). A well-defined GQDs must be produced by
extracting sp2 domains from oxidized graphene sheet via a bond
scission of surrounding oxygen groups. To extract sp2 domains
without deconstructing their graphitic structure, we developed
a soft self-limiting bond-scission process. In fact, OGSs were
subjected to mild amino-hydrothermal treatment at 70–150 °C
using ammonia solution, followed by thermal annealing at
100 °C. In the treatment of OGSs, ammonia reacts with epoxy
groups to form a primary amine and alcohols by nucleophilic
substitution (Supporting Figure S3a),[16,17] and thus it enables
self-limited extraction of the sp2 domains by ring-opening of
the epoxide and the simultaneous direct bonding of a primary
amine with a graphene edge. Consequently, size-controlled
GQDs that are edge-terminated with a primary amine are pro-
duced, as confirmed by the structural analyses (Figure 1b, 1c,
Figure 2 and Supporting Figure S4, S5).
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Figure 1. a) Schematic illustration of the preparative strategy for af-GQDs. b) C1s and N1s X-ray photoelectron spectra for af-GQDs prepared at
90 °C (green line) and OGS (gray line). The pronounced decrease in the C 1s signal at 286.4 eV, which is assigned to epoxide groups, is a manifesta-
tion of the loss of epoxides through nucleophilic reaction with ammonia. This interpretation is supported by the appearance of the N 1s signal at
399.7 eV, which is assigned to primary amines (⫺NH2) bonded to the graphene. c) Transmission infrared-absorbance spectra of af-GQDs prepared
at 90 °C (green line) and OGS (gray line). New peaks at 1243, 1617, and 3300–3600 cm−1 appeared after the amino-hydrothermal treatment. These
peaks were assigned, respectively, to C⫺N in-plane, N⫺H out-of-plane, and N⫺H in-plane stretching of the amine groups. Additionally, characteristic
amide–carbonyl (⫺NH⫺CO⫺) stretching vibration was observed at 1650 cm−1, which implies the formation of amide groups through interactions
with the carboxylic groups as Lewis acids.

Transmission electron microscopy (TEM) images veri-
fied the production of uniform af-GQDs with a diameter of
∼2.5 nm (Figure 2a, 2c and Figure S5). No noticeable change
was observed in their size and shapes for the af-GQDs prepared
at 70–120 °C, while high temperature amino-hydrothermal
treatment (>150 °C) induced the fragmentation into smaller
sizes (Figure S5). The corresponding atomic Force Microscope
(AFM) image (Figure 2b and 2d) revealed that most of af-GQDs
have a thickness of ∼1.13 nm, which corresponds to single-
layer of functionalized graphene quantum dots.[2,6,12] Raman
spectrum also provided convincing evidence for the graphene
fragment structure of the af-GQDs. The peak at ∼1600 cm−1 (G)
corresponds to the E2g mode of graphite and is related to the
vibration of the sp2-bonded C atoms in a two-dimensional hex-
agonal lattice, while the peak at ∼1370 cm−1 (D) exhibits disorder
due to scattering at the edges (Figure 2e). The relative inten-
sity of D/G band is ∼0.6, similar to that of electrochemically-
derived graphene quantum dots[2,12] and few-layer graphene
nanoribbons,[18,19] which indicates the high quality of af-GQDs.
Figure 2f gives X-ray diffraction (XRD) patterns of the af-GQDs
prepared at 90 °C and OGSs dried powders. A weak broad (002)
peak centred at 2θ = ∼22.7° and a disappearance of peak at
2θ = ∼10.6° in the spectrum for af-GQDs indicate the disor-
dered stacking structures of graphene layers and the absence of
oxygen functional groups in between interlayers, respectively.
The XRD and AFM results suggest the formation of exfoli-
ated monolayer graphene layers.[20] Moreover, as confirmed by
X-ray photoelectron spectroscopy (XPS) and Fourier transform
infrared spectroscopy (FT-IR) analyses, the produced af-GQDs
contain large amount of amino-groups (Figure 1b and 1c).
Therefore, it is supposed that there is no significant basal plane
functionalization, and hence the amino-groups might be pre-
ponderantly located in the edges of graphene layers.
The extracted af-GQDs exhibit efficient photoluminescence,
and their fluorescence can be tuned from the violet to the yellow
region thorough the functionalization of the primary amine.
The degree of amine functionalization, which controls the photo-
luminescence color, can be controlled simply by changing the
initial concentration of ammonia and the temperature of the
amino-hydrothermal treatment (Supporting Figure S4). It was
found that low temperature synthesis is needed for successful
amine functionalization. Higher temperature, i.e. >120 °C,
induces dissociation of primary amine after nucleophilic reac-
tions with ammonia, resulting lower C/N ratio. The thermal
stability of amine-functional group on af-GQDs was evalu-
ated using thermogravimetric analysis (Supporting Figure S6).
Figures 3a and 3b show the emission images and fluorescence
spectra from af-GQDs. Aqueous suspensions of af-GQDs exhibit
bright colorful luminescence under irradiation from a UV lamp
with a wavelength of 365 nm (upper images of Figure 3a); their
corresponding emission peaks vary with the quantity of amine
functionalization in the range of 420–535 nm and retain a sharp
full-width at half-maximum (FWHM) as narrow as ∼65–80 nm.
A clear red shift of absorption band with the quantity of amine
functionalization was also observed in the UV-visible absorp-
tion spectra of af-GQDs. For GQDs, the optical properties are
known to be dictated by a combination of a couple of factors,
i.e., size, shape, and surface functionality of GQDs. Because the
af-GQDs prepared at 70–120 °C have almost same shape and
size, the tunable photoluminescence should be originated only
from the difference in the quantity of functionalized amine-
groups, at least in the blue to yellow region. The emission

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Figure 2. a) TEM image of the af-GQDs prepared at 90 °C. b) AFM image of the af-GQDs
prepared at 90 °C on mica substrate. The inset shows the height profile along the line. amino-hydrothermal treatment, showed a
c) The size distributions of af-GQDs. The average size is ∼2.5 nm. d) The height distributions broad mass spectrum with no regularity
of af-GQDs. The average height is ∼1.13 nm. e) Raman spectrum of the af-GQDs prepared (Figure S9) because of ‘non-selective’ frag-
at 90 °C. f) XRD patterns of the af-GQDs prepared at 90 °C and OGSs dried powders.
wavelength increased with the contents of amine-groups. For
af-GQDs prepared at 150 °C, on the other hand, size effect may
also make an important contribution to the observed violet
emission, because the optical band gap should be increased
with decreasing sp2 domain size due to the quantum confine-
ment effects.[9,21] The photoluminescence quantum yield (QY)
calibrated against quinine sulphate as a standard sample (54%
in 0.5 M H2SO4) was found to be ∼29–19%, which decreased
with quantity of amine functionalization. This is much higher
than that of previously reported GQDs (typically <10%). The
high PL QYs may be attributed to the chemical nature of af-
GQDs. The af-GQDs contain less carboxylic and epoxide groups
acting as the non-radiative electron-hole recombination centers,
which leads to the efficient emission. Furthermore, surface
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passivation with polyethylene glycol sig-
nificantly enhanced the photoluminescence
QY to ∼46%, by the stabilization effect of
excitons in the GQDs.[22] Our af-GQDs also
exhibit excellent compatibility with various
organic polymers, which enables their incor-
poration into solid matrices without further
chemical modifications. The bottom images
in Figure 3a show flexible polydimethylsi-
loxane (PDMS) elastomer with a luminescent
piece of af-GQDs@PDMS hybrid patterned
in the logo of our institute. The af-GQDs
retain their fluorescent properties upon inte-
gration into polymer matrices without any
noticeable change in the shape or FWHM of
their emission spectrum peaks (Supporting
Figure S7), suggesting that no significant
surface deterioration or aggregation of the
af-GQDs occurred.
Mass spectrometry using the matrix-
assisted laser desorption/ionization reflec-
tron time-of-flight technique (MALDI-
TOF mass) revealed their narrow size
distribution and unique edge structures. The
af-GQDs prepared at 70–120 °C display similar
masses, consistent with the TEM observation
showing a rather uniform size of af-GQDs
to be ∼2.5 nm. To our surprise, regular pat-
terns with the repeating unit of m/z 74
were observed between m/z 1200 and 2500
in the mass spectrum of af-GQDs prepared
at 120 °C (Figure 4a). Amino-hydrothermal
treatment at temperatures greater than
150 °C induces breakage into smaller frag-
ments with no regular mass pattern (Sup-
porting Figure S8). To our knowledge, such
a regular pattern has never been previously
reported in a mass spectrum for graphene or
graphene oxide. Starting OGSs, purified via
same purification process without applying
mentation. This fact confirms the selective
fragmentation of af-GQDs with specific edges
and size. We attribute this repeating unit of m/z 74 to the reflec-
tion of their edge structure, which were verified by optimised
geometric calculations based on molecular mechanics methods
using augmented MM3 parameters (details in Supporting
Information). The mass of 74 is expected to be a six-membered
C ring bonded to an armchair edge of an af-GQD (schematically
shown in the inset of Figure 4a): 74 Δm = –[loss of two-coordinate
six-membered C ring bonded to an armchair edge (Mw = 76)] +
[termination of two hydrogen atoms (Mw = 2)]. Here, we con-
sider two types of bonds in the armchair-edged GQDs: one
directed nearly along the axis, CCa, and another directed along
the circumference, CCc (Supporting Figure S10). The optimised
geometric calculations predict that the GQDs structure without
outermost CCc bonds are more stable than that without the CCa
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The different luminescence colors

should originate from a change in the
electronic structure of the af-GQDs. It has
been reported that N doping in pyridinic
sites induces blue shift in photolumines-
cence maximum because of high elec-
tronic affinity of the nitrogen atom.[12]
This behavior is inconsistent with our
tendency. To elucidate this point, we per-
formed ab initio calculations using the
plane-wave projector augmented wave
(PAW) method (details in Supporting
Information).[23,24] Based on the MALDI-
TOF mass, IR, and XPS structural anal-
yses, we modelled a graphene structure
Figure 3. a) Emission images of af-GQDs dispersed in water (upper) and af-GQD@polymer with two-coordinate six-membered C rings
hybrids (bottom) under irradiation from a 365 nm UV lamp. The af-GQDs in the upper images connected to armchair edges, as illus-
were prepared under the following conditions: 150 °C, 120 °C, 70 °C, 90 °C, and 90 °C in ×2
trated in Figure 4c. This figure also shows
conc. ammonia solution, respectively from the left. The bottom images show flexible poly-
dimethylsiloxane (PDMS) elastomer with a luminescent piece of af-GQDs@PDMS hybrid pat- the isosurfaces of the highest occupied
terned in the logo of our institute. b) Photoluminescence and selected UV/VIS absorption molecular orbital (HOMO) and the lowest
spectra of af-GQDs. The photoluminescence spectra are those of the af-GQDs shown in the unoccupied molecular orbital (LUMO)
upper image of Figure 1a. In the absorption spectra, solid and broken lines denote the spectra (details in Supporting Figure S13). The
of af-GQDs prepared at 120 °C and 90 °C, respectively. influence on the optical properties of af-
GQDs of the adsorption of primary amine
bonds, which results in one- or two-coordinate six-membered groups on their edges was investigated. A primary amine
C rings bonded to an inner armchair edge. The structure with at the edge significantly alters the whole electronic struc-
two-coordinate C ring at armchair edge is thermodynamically ture of an af-GQD; one of the degenerate HOMO orbitals
less stable than those with a one-coordinate ring, with a differ- in the hydrogen-terminated graphene molecule is lifted to a
ence in energy of 0.48 eV. The loss of two-coordinate C ring is higher energy in the af-GQD as a consequence of a strong
vital to cause the difference of m/z 74 in the mass pattern orbital interaction with the ⫺NH 2 amino group. This
(Supporting Figure S11). interaction results in a narrowing of the optical band gap
Intriguingly, the mass pattern from af-GQDs prepared at (Supporting Figure S14). The optical band gap decreases
90 °C shifted to a higher mass by precisely m/z 29 and retained with the quantity of primary amine. The amount of the
the regularity of the repeating m/z 74 unit, as shown in Figure 4b. bandgap narrowing is rather independent of the size of
The difference of m/z 29 is attributable to the attachment the molecules, confirmed by different size of models, C6H6
of additional functional groups at the two-coordinate C-ring to C36H 18 (Supporting Table S1). Looking into other func-
edge sites. FT-IR analysis showed a distinct increase in the tional groups such as ⫺CH3 and ⫺NO, we observed that
intensity of the N-H stretching signal and an appearance of the former affects neither the HOMO nor the LUMO. We
the C⫺H (⫺CH3) stretching signal from af-GQDs prepared also observed that ⫺NO induces states in the bandgap that
at 90 °C. XPS measurements also revealed that the C to N are characterized by localization in the NO group and by
molar ratio decreased to 8.3:1 for the sample prepared at 90 °C no sign of strong interaction with the original graphene
from 26:1 for the sample prepared at 120 °C. Consequently, orbitals (Supporting Figure S15). The resonance feature
the additional functional groups are assumed to at least have between the delocalized π orbital and the molecular orbital
amino group, i.e., ⫺NH2/⫺CH3 pair. The ⫺NH2/⫺CH3 pair to in the ⫺NH 2 amino group is thus an origin of both the
be attached into the two-coordinate C-ring sites, as estimated edge-treatment-dominated optical tunability and the high
from consideration of the mass difference: the attachment of quantum efficiency that is observed experimentally. In
⫺NH2/⫺CH3 pair at the two-coordinate C ring induces the addition, such a resonance orbital can lead to the process
molecular weight by 29 mass unit, while the bonding into of intersystem crossing emission as a result of enhanced
basal plane of af-GQDs makes 31 mass difference. Importantly, spin–orbital coupling. In fact, we observed extraordinary
the corresponding emission color of the af-GQDs switched long delayed luminescence of sub-second order from
to green from blue after this functionalization (shown in af-GQDs (details in Supplementary Figure S15).
the inset of Figure 4b). This result implies that the lumines- In summary, we have demonstrated novel amino-functional-
cence in af-GQDs is greatly affected by the edge structure ized GQDs with high efficiency and wide tunability of narrow
because no difference in size or shape was observed. This photoluminescence lines under a single-wavelength UV excita-
supposition is supported by the fact that blue and green tion, whose energy are controlled by their edge-termination
af-GQDs can be distinguished only using chromatographic structure with primary amine. Their superior optical properties
technique, which separates af-GQDs into different polarities should enable the use of af-GQDs in numerous applications,
depending on their degree of amino-functionalization at the including multicolor light-emitting devices, biological applica-
edge (Supporting Figure S12). tions, and photovoltaics.

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Figure 4. a) MALDI-TOF mass spectrum of af-GQDs in aqueous solution prepared at 120 °C. Note that peaks are detected as Na ion adducts ([M +
Na]+), the Na ion of which might have originated from residue in the reagents used for graphite oxidation to prepare the graphene oxide. Inset, sche-
matic representation of the edge structure of the af-GQDs. b) Comparison of MALDI-TOF mass spectra for af-GQDs prepared at 120 °C (bottom)
and 90 °C (upper). The inset shows the possible edge structures and their photoluminescence spectra excited at 350 nm. c) Schematic illustrations of
structures used for theoretical calculations with different functional groups. The isosurface represents the highest occupied molecular orbital (HOMO)
and the lowest unoccupied molecular orbital (LUMO). I: hydrogen-terminated edge structure, II: ⫺NH2/⫺CH3 pair bonded to edge. The unit of energy
is electron volt (eV).

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