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A study of graphenes prepared by different methods: characterization,

properties and solubilization†‡
K. S. Subrahmanyam, S. R. C. Vivekchand, A. Govindaraj and C. N. R. Rao*
Received 26th October 2007, Accepted 6th December 2007
First published as an Advance Article on the web 7th January 2008
DOI: 10.1039/b716536f
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Graphene has been prepared by different methods: pyrolysis of camphor under reducing conditions
(CG), exfoliation of graphitic oxide (EG), conversion of nanodiamond (DG) and arc evaporation of
SiC (SG). The samples were examined by X-ray diffraction (XRD), transmission electron microscopy,
atomic force microscopy, Raman spectroscopy and magnetic measurements. Raman spectroscopy
shows EG and DG to exhibit smaller in-plane crystallite sizes, but in combination with XRD results
EG comes out to be better. The CG, EG and DG samples prepared by us have BET surface areas of 46,
925 and 520 m2 g
1 respectively and exhibit significant hydrogen uptake up to 3 wt%. EG also exhibits
a high CO2 uptake (34.7 wt%). Electrochemical redox properties of the graphene samples have been
examined in addition to their use in electrochemical supercapacitors. Functionalization of EG and DG
through amidation has been carried out with the purpose of solubilizing them in non-polar solvents.
Water-soluble graphene has been produced by extensive acid treatment of EG or treatment with
polyethylene glycol.

Introduction after characterizing them. We have been able to carry out a

Graphene has emerged to be an exciting material with potential
applications.1,2 A remarkable feature of graphene is that it is
a Dirac solid, with the electron energy being linearly dependent
on the wave vector near the crossing points in the Brillouin
zone. It also exhibits unusual fractional quantum Hall effect
and conductivity behavior. Most physical studies of graphene
are carried out on sheets obtained by the ‘scotch-tape’ technique,
wherein a single graphene sheet is removed at a time from highly
ordered pyrolytic graphite. This method obviously cannot be
employed for large-scale applications or to study many of the
chemical and materials properties of graphene. Laboratory
synthesis of graphene has been carried out by a few workers.
The methods employed include (a) pyrolysis of camphor under
reducing conditions,3 (b) exfoliation of graphitic oxide,4 and (c)
conversion of nanodiamond.5 An examination of the literature
shows that graphene samples prepared by the different methods
have not been fully characterized. It is indeed necessary to know
the best and most straightforward method(s) to characterize
graphene samples and also to have a comparative evaluation
of the quality and the characteristics of graphenes obtained by
the different preparative methods, to be able to make the right
choices. We have, therefore, prepared graphene by employing
the three methods mentioned above, designated as CG, EG
and DG respectively, and investigated some of their properties
Chemistry and Physics of Materials Unit, CSIR-Centre of Excellence in
Chemistry and DST Unit on nanoscience, Jawaharlal Nehru Centre for
Advanced Scientific Research, Jakkur PO, Bangalore, 560 064, India.
E-mail: cnrrao@jncasr.ac.in; Fax: +91 80 2208 2760
† This paper is part of a Journal of Materials Chemistry theme issue on
carbon nanostructures.
‡ Electronic supplementary information (ESI) available:
Thermogravimetric analysis of EG, DG and CG in an oxygen
atmosphere. See DOI: 10.1039/b716536f
preliminary study of graphene prepared by the arc evaporation
of SiC (SG).6 For the purpose of characterization, we have
employed X-ray diffraction, transmission electron microscopy,
atomic force microscopy and Raman spectroscopy. Raman
spectroscopy is especially useful in determining the in-plane
crystallite size of the graphene samples.7–9 Our Raman and other
studies revealed EG and DG to possess not only a smaller
in-plane crystallite size but also desirable properties. We have
measured the surface areas and hydrogen uptake of these
samples and determined their electrochemical properties includ-
ing their possible application in electrochemical supercapacitors.
Cyclic voltammetric studies reveal that EG exhibits redox
behavior similar to that of the basal planes of graphite. Electro-
chemical supercapacitors fabricated by using an ionic liquid
enable a large operating voltage of 3.5 V to be employed and
give rise to high values of specific capacitance and energy density.
We have carried out investigations on the functionalization and
solubilization of EG and DG using methods similar to those
reported for carbon nanotubes,10–12 since such dispersions would
be required in many applications and manipulations. It was of
interest to us to solubilize graphene in non-polar solvents as
well as water.
Experimental
Graphene was prepared by four different methods, namely the
reductive pyrolysis of camphor (CG),3 exfoliation of graphitic
oxide (EG),4 conversion of nanodiamond (DG)5 and arc
evaporation of SiC (SG).6 In the first method, to prepare CG,
camphor was pyrolysed over nickel particles under a reducing
atmosphere. The reaction was carried out in a two-stage furnace
and camphor was slowly sublimed (170  C) by heating from the
first furnace to the second furnace held at 770  C where the

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micron sized nickel particles were placed. The second method to
prepare EG involved the thermal exfoliation of graphitic oxide.
In this method, graphitic oxide was prepared by reacting
graphite (Alfa Aesar, 2–15 mm) with a mixture of conc. nitric
acid and sulfuric acid with potassium chlorate at room tempera-
ture for 5 days. Thermal exfoliation of graphitic oxide was carried
out in a long quartz tube at 1050  C under an Ar atmosphere.
Thermal conversion of nanodiamond (particle size 4–6 nm,
Tokyo Diamond Tools, Tokyo, Japan) to graphene was carried
out at 1650  C in a helium atmosphere to obtain DG. In the
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specific capacitance is given by the following equation: CCV ¼
2(i+
i
)/(m  scan rate), where i+ and i
are the maximum
currents in the positive scan and the negative scan respectively
and m is the mass of the electrode. The energy density is given as
E ¼ CV2, where C is the capacitance taking into account both
the electrode masses and V is the operational voltage.
To solubilize graphene samples (EG and DG) in non-polar
solvents the following procedure was employed. In the first
step, conc. nitric acid (2 mL), conc. sulfuric acid (2 mL) and
water (16 mL) were added to graphene (50 mg) and subsequently

last method, SG was obtained by arc evaporation of SiC (arc- heated in a microwave oven for 10 min under hydrothermal
melted mixture of Si and graphite) in a hydrogen atmosphere conditions. Further, the sample was heated at 100  C for 12 h.
(200 Torr) with a DC current of 45 A and 38 V. The product was washed with distilled water and centrifuged
The samples were characterized using transmission electron repeatedly to remove traces of acid. This yielded graphene that
microscopy (TEM), atomic force microscopy (AFM), X-ray was functionalized with –OH and –COOH groups. The acid
diffraction (XRD) and thermogravimetric analysis. Raman treated graphene was refluxed with excess SOCl2 for 12 h and
spectra were recorded at different locations of the sample using the unreacted SOCl2 was removed under vacuum. The product
a Jobin Yvon LabRam HR spectrometer with a 514 nm Ar laser. was treated with dodecylamine (5 mL) under solvothermal
TEM images were obtained with a JEOL JEM 3010 instrument conditions at 100  C.
fitted with a Gatan CCD camera operating at an accelerating In order to solubilize graphene in water, EG was further
voltage of 300 kV. AFM measurements were performed using treated with a (1 : 1) mixture of conc. nitric acid and sulfuric
a CP 2 atomic force microscope. Thermogravimetric analysis acid at 100  C. This gave some water-soluble graphene in addi-
of the samples was carried out in a flowing oxygen atmosphere tion to an insoluble fraction. To prepare water soluble graphene,
with a heating rate of 10  C min
1 using a Mettler-Toledo-TG- another procedure was also employed. Here, polyethylene glycol
850 apparatus. Infrared (IR) spectra were recorded on small (PEG)-functionalized EG was prepared by reacting acid treated
pieces of the samples embedded in KBr pellets using a Bruker graphene with excess of PEG (6 mL) and conc. HCl (2 mL) under
FT-IR spectrometer. Magnetization measurements were carried solvothermal conditions at 100  C for 12 h.
out with a vibrating sample magnetometer in a physical
properties measuring system (PPMS, Quantum Design, San Results and discussion
Diego, CA, USA).
Surface area measurements and low-pressure hydrogen Characterization
up-take experiments were carried out with a QuantaChrome In Fig. 1, we show typical TEM images of the different graphene
Autosorb-1 instrument. High pressure hydrogen adsorption samples, CG, EG, DG and SG, prepared by us. Large crystalline
experiments were performed using a home-built adsorption
set-up as reported by Gundiah et al.13 The experiments were
performed at 300 K and 100 bar using ultra high pure hydrogen
(99.99%), with an impurity (e.g. moisture and nitrogen) content
of less than 10 ppm. The graphene samples were accurately
weighed (in excess of 100 mg) and taken into the sample cell.
The sample cell was evacuated to 10
5 Torr and heated for 12 h
at 125  C in order to degas the sample before the adsorption study.
Electrochemical measurements were performed using a
PG262A potentiostat/galvanostat (Technoscience Ltd, Banga-
lore, India). Voltammetric properties of graphenes were investi-
gated using a three electrode electrochemical cell containing
a graphene paste electrode, platinum foil as the counter electrode
and calomel as the reference electrode using 1M KCl solution
containing 100 mM potassium ferrocyanide. All graphene paste
electrodes were prepared using mineral oil as a binder
(25 wt%).14 Graphene-based supercapacitor cells were fabricated
following Conway.15 The measurements were carried out with
a two-electrode configuration, the mass of each electrode being
5 mg and the ionic liquid, N-butyl-N-methylpyrrolidinium bis(tri-
fluoromethanesulfonyl)imide (PYR14TFSI) was dried at 80  C
under vacuum for a day prior to the experiment. The fabrication
and characterization of cell was done at 60  C in a mBraun glove Fig. 1 TEM images of graphene obtained by (a) reductive pyrolysis of
box keeping the oxygen and water levels at less that 0.1 ppm. We camphor (CG), (b) thermal exfoliation of graphitic oxide (EG), (c)
have performed cyclic voltammetry to characterize the two- thermal conversion of nanodiamond to graphene (DG) and (d) arc
electrode supercapacitor cells with the different graphenes. The evaporation of SiC (SG).

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Fig. 3 Typical AFM images and height profiles of graphene samples: (a)
CG, (b) EG and (c) DG.
Fig. 2 (a) X-Ray diffraction patterns of the CG, EG and DG. (b)
Lorentzian fit for (002) and (c) double Lorentzian fit for (100) and
from the (100) reflection. The (100) reflection is overlapped by
(101) diffraction peaks for DG.
the (101) reflection and had to be deconvoluted to obtain the
position and width. The in-plane approximate crystallite sizes
sheets are observed in the case of CG, while disordered graphene
for CG, EG and DG are 6.1, 4.7 and 5.0 nm respectively.
sheets are seen in EG as can be seen from Fig. 1 (a) and (b)
We have carried out AFM studies at different locations of CG,
respectively. Small particles with diameters in the 3–20 nm range
EG and DG. We show typical AFM images of these graphenes in
along with onion-like nanoparticles are found in the TEM image
Fig. 3. AFM cross-section height profile analysis indicates that
of DG in Fig. 1(c). The TEM image of SG shows few-layered
the CG sample consists of more than 20 layers while EG and
graphene sheets as seen in Fig. 1(d). The XRD patterns of CG,
DG possess 3 to 6 graphene layers.
EG and DG are shown in Fig. 2. The sharp graphitic reflection
Raman spectroscopy is a most useful tool to characterize
in the powder X-ray diffraction pattern of CG shows that it is
graphene. A single layer graphene shows the well-known
comprised of a large number of layers. EG shows broad peaks
G-band around 1560 cm
1 and a band around 1620 cm
1 (D0 ).
in the XRD pattern. The XRD pattern of DG reveals that it
The D0 band is defect induced and not found in graphite. The
contains reflections corresponding to both small and large
D-band around 1350 cm
1 arising from disorder is very weak
graphitic particles. We have fitted the (002) and (100) profiles
in a single layer graphene and increases in intensity with the
to obtain the number of layers and the in-plane crystallite size
number of layers. The 2D band (2600 cm
1) which appears in
of the graphene samples (see Table 1). By fitting the (002) reflec-
single layer graphene is also sensitive to the number of layers
tion, one can obtain the average number of layers using the
and shows greater structure (often a doublet) with increasing
Scherrer formula. In Fig. 2(b), we show a typical multiple
number of layers. In Fig. 4, we show typical Raman spectra
Lorentzian fit for the (002) reflection in the case of DG. CG
for the graphene samples taken at two different locations and
primarily consists of 51 layers. The number of layers in EG
in Table 2, we summarize the Raman band positions with assign-
is found to be 3 and 16 while in DG it is 6 and 87. We have
ments. We see that the D-band is quite intense compared to the
calculated the in-plane crystallite size of the various graphenes
G-band, especially in EG and DG. The ratio of the intensity of
the G-band to the D-band is related to the in-plane crystallite
Table 1 Number of layers and crystallite size from the X-ray diffraction size, La. We have calculated the in-plane crystallite size from
patterns of the graphene samples
the spectra taken at various locations of the graphene samples
Number of layers from Crystallite size from by employing the ratio, La¼ 4.4(IG/ID)8,9 (Table 3). CG shows
Sample (002) reflectiona (100) reflection/nm the largest La and DG the smallest with EG falling in between
DG and CG. Preliminary studies indicate that the La of SG is
CG 51 6.1
around 4. One may therefore consider EG and DG to be the
EG 3, 16 4.7
DG 6, 87 5.0 samples best suited for further study of various chemical and
a
electrochemical properties. However, if one takes the XRD
Two values given below are obtained from fits to the two (002) profiles
in the XRD patterns
results (Table 1) into account, EG would be superior to DG. It
is noteworthy that the position of the G-band varied in the order

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Table 3 In-plane crystallite sizes, La (in nm) of the graphene samples es-
timated from IG/ID ratios in the Raman spectraa

Sample IG/ID La

CG 1.5, 2.4, 2.8 7, 10, 12

EG 1.0, 1.4, 1.7 4, 6, 7
DG 0.8, 0.8, 1.1 3, 4, 5
a
The different IG/ID values are from different locations in the sample. A
preliminary study of SG gives La ¼ 4.
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oxidation temperature of 520  C, exhibiting a sharp mass

loss at this temperature followed by a gradual mass loss. The
low oxidation temperature of EG is ascribed to the presence of
functional groups while the other graphenes consist of pure
carbon and are more crystalline in nature as observed in the
X-ray diffraction patterns.

Gas adsorption
The Brunauer–Emmett–Teller (BET) nitrogen adsorption
isotherms for EG and DG are shown in Fig. 5. Both the samples
exhibit Type I + Type II behavior and their surface areas are 925
and 520 m2 g
1 respectively. The pore size distributions of the
samples are shown as insets in Fig. 5, and reveal that EG is

Fig. 4 Raman spectra for CG, EG and DG recorded at different loca-

tions (a) and (b) using 514 nm laser excitation.

DG > EG > CG. It is known that the G-band position increases

with decreasing number of layers.7–9 The observed trend in the
G-band frequency is consistent with the La values calculated
from the IG/ID intensity ratios (Table 3).
Magnetic susceptibility measurements in the 1–300 K range
show that both EG and DG exhibit Curie behavior. The suscep-
tibility values of EG and DG at 300 K are
3.5  10
6 and
4.4
 10
6 emu g
1. These data are comparable to those reported by
Andersson et al.5
The thermogravimetric analysis of CG, EG and DG was
carried out. CG undergoes sharp oxidation around 730  C while
DG gets oxidized at 700  C (see ESI‡). EG exhibits the lowest

Table 2 Raman bands (in cm
1) of graphene samplesa

Sample D G G’ 2D D+G

CG (a) 1321 1567 1604 2647 2919

(b) 1342 1569 1605 2687 2920
EG (a) 1324 1569 1605 2652 2908
(b) 1352 1574 1608 2705 2926
DG (a) 1332 1576 1606 2678 2909
(b) 1330 1576 1608 2682 2905
a
(a) and (b) represent data taken from different locations Fig. 5 Nitrogen adsorption isotherms of (a) EG and (b) DG with the
insets showing pore size distributions.

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Electrochemistry

We have investigated the electrochemical properties of CG, EG

and DG using the redox reactions with potassium ferrocyanide.
The peak to peak separation is known to be significantly depen-
dent on the microstructure of the carbon electrode used.17 A
small peak to peak separation (70 mV) is achieved when the
edges of graphite are exposed to the electrolyte, while it is signifi-
cantly larger (even close to 1 V) when the basal planes are
involved. In Fig. 7(a), we show typical cyclic voltammograms
of the redox reaction of 100 mM potassium ferrocyanide (in
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1 M KCl) carried out using working electrodes of different

graphenes. While the peak to peak separation depends on the
scan rate, it is found to be the largest in the case of EG. DG
and CG exhibit similar peak separations. The behavior of EG
is similar to that of the basal plane in graphite. On the other
hand, DG and CG exhibit slightly better kinetics.
We fabricated supercapacitor cells with water as well as an
ionic liquid, N-butyl-N-methylpyrrolidinium bis(trifluorometha-
nesulfonyl)imide (PYR14TFSI), as electrolytes. EG and DG
exhibit specific capacitances of 117 and 35 F g
1 respectively in

Fig. 6 Hydrogen uptake of (a) EG and (b) DG at 77 K with the insets

showing high pressure hydrogen adsorption at 100 bar.

mesoporous with pores greater than 3 nm while DG has both

micropores and mesopores. CG exhibited a rather low surface
area of 46 m2 g
1. Single layer graphene is estimated to have a
surface area of 2600 m2 g
1, thereby indicating that both EG
and DG consist of more than one layer as indeed found from
Raman and other studies.
We have investigated the hydrogen uptake of EG and DG as
they possess large surface areas. The hydrogen adsorption
studies were carried out under two different experimental condi-
tions, the first at 1 atm and 77 K and the second experiment at
high pressures and 300 K. By the first method, we found that
EG and DG can adsorb 1.38 and 0.68 wt% of hydrogen (Fig. 6).
These graphene samples showed significantly higher adsorption
in the high pressure experiments, yielding 3.1 and 2.5 wt% respec-
tively for EG and DG (see insets in Fig. 6). The adsorption is
completely reversible and comparable to that of carbon nano-
tubes15 and porous open framework materials.16 Though the
graphene samples examined by us exhibit lower hydrogen uptake
compared to the 6.0 wt% target of the Department of Energy Fig. 7 (a) Cyclic voltammograms of the different graphene electrodes
(USA), there is significant scope for further improvements, by (at a scan rate of 20 mV s
1) for 100mM K4Fe(CN)6 in 1 M KCl and
producing samples with smaller number of layers and significantly (b) voltammetry characteristics of a capacitor built from an EG electrode
higher surface areas. EG is also a good adsorbent for CO2, the at a scan rate of 100 mV s
1 using PYR14TFSI. Inset shows the specific
uptake going up to 34.7 wt% at 195 K and 1 atm. capacitance as a function of scan rate.

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aq. H2SO4 with an operational voltage of 1 V. When we used
PYR14TFSI, we could achieve a significantly higher operating
voltage of 3.5 V compared to that in aq. H2SO4 due to the large
electrochemical window of the ionic liquid. In Fig. 7(a), we show
a typical CV of a graphene–PYR14TFSI supercapacitor obtained
at a scan rate of 100 mV s
1. A specific capacitance value of 75 F
g
1 was obtained with EG. The specific capacitance depends
significantly on the scan rate as the ionic liquid is highly viscous
(inset in Fig. 7(b)). The maximum value of energy density stored
in these capacitors are 31.9 Wh kg
1. This is one of the highest
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values reported to date and is comparable to those of micro-
porous carbons reported by Balducci et al.18
Functionalization and solubilization
As-prepared EG shows evidence for the presence of carbonyl
and hydroxyl groups on the surface. After further treatment of
EG with a nitric and sulfuric acid mixture, we obtained a water
solution of EG, along with the insoluble portion of the sample
which settled out. The infrared (IR) spectrum of the soluble
part obtained after drying shows a prominent band due to
carbonyl groups in addition to a broad band due to –OH groups
as shown in Fig. 8(a). The Raman spectrum of the water-soluble
EG shown in Fig. 8(b) exhibits the characteristic G, D and 2D
Fig. 8 (a) Infrared and (b) Raman spectra of water-soluble EG. Inset
shows photographs of water-soluble (H2O) and PEG-functionalized
EG dispersed in water (PEG).
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bands and show that La of the sample is 4 on an average (as
calculated from the intensity ratio of the D and G bands). In
the inset of Fig 8(b), we show a photograph of the water-soluble
graphene. The water-insoluble EG when treated with polyethyl-
ene glycol (PEG) yielded water-dispersible graphene. In the inset
of Fig. 8(b), we also show a photograph of the water-dispersion
of PEG-treated graphene.
By carrying out the amidation reaction similar to that reported
for carbon nanotubes, we obtained dispersions of EG in various
non-polar solvents. The results are similar to those reported by
Haddon and co-workers.19 In Fig. 9(a), we show photographs
of the dispersions of dodecylamide-functionalized EG in
dichloromethane, carbon tetrachloride and tetrahydrofuran. In
Fig. 9(b), we show photographs of the dispersions prepared
with DG. It should be noted, however, that DG requires hasher
acid treatment and over longer periods to enable further
functionalization to be carried out. In Fig. 9(c), we show the
infrared spectra of EG at various stages of the solubilization
process. After acid treatment, EG show a carbonyl stretching
band at 1710 cm
1 due to the carboxyl groups. On functionaliza-
tion with dodecylamine, the C]O stretching band shifts to 1650
cm
1 due to the amide band, in addition to C–H and N–H
stretching bands around 2800 and 3300 cm
1 respectively.
Fig. 9 Photographs of dispersions of (a) the amide-functionalized EG in
THF, CCl4 and dichloromethane, (b) amide-functionalized DG in THF,
CCl4 and dichloromethane. (c) Infrared spectra of pristine EG, acid-
treated EG (EG-COOH) and amide-functionalized EG (EG-amide).
This journal is ª The Royal Society of Chemistry 2008

Conclusions
In conclusion, a comparative study of graphene samples
prepared by different methods has been carried out. In terms
of the number of layers, crystallite size as well as surface area,
graphene prepared by the exfoliation of graphite (EG) seems
to be best, possessing high surface area and a smaller number
of layers. Graphene prepared by conversion of nanodiamond
(DG) is also satisfactory and has greater thermal stability than
EG. Both EG and DG exhibit significant hydrogen uptake.
EG shows electrochemical redox behavior similar to that of
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the basal plane of graphite and can be used for fabrication of
electrochemical supercapacitors. Acid-treated EG and DG can
both be solubilized in non-polar solvents by reaction with
thionyl chloride followed by dodecylamine. Water-soluble EG
could be prepared by extensive acid treatment or treatment
with polyethylene glycol.
Acknowledgements
The authors acknowledge the help of Mr Saikrishna for surface
area and low-pressure hydrogen adsorption measurements and
Dr Sundaresan for magnetic measurements.
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