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Fullerenes, Nanotubes and Carbon

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Characterization of Graphene
Nanoribbons from the Unzipping of
MWCNTs
Franco Cataldo

a b

, Giuseppe Compagnini , Luisa D'Urso ,

b

Giuseppe Palleschi , Federica Valentini , Giancarlo Angelini &

Tibor Braun

Lupi Chemical Research, Rome, Italy

Department of Chemistry, Tor Vergata University, Rome, Italy

Dipartimento di Scienze Chimiche, Universit di Catania, Catania,

Italy
d

CNR, Institute of Chemical Metodologies, Monterotondo Scalo

(Rome), Italy
e

Institute of Chemistry, L. Eotvos University, Budapest, Hungary

Available online: 29 Jun 2010

To cite this article: Franco Cataldo, Giuseppe Compagnini, Luisa D'Urso, Giuseppe Palleschi, Federica
Valentini, Giancarlo Angelini & Tibor Braun (2010): Characterization of Graphene Nanoribbons from
the Unzipping of MWCNTs, Fullerenes, Nanotubes and Carbon Nanostructures, 18:3, 261-272
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Fullerenes, Nanotubes, and Carbon Nanostructures, 18: 261272, 2010

Copyright Taylor & Francis Group, LLC
ISSN: 1536-383X print / 1536-4046 online
DOI: 10.1080/15363831003782981

Characterization of Graphene Nanoribbons

from the Unzipping of MWCNTs
FRANCO CATALDO1,2, GIUSEPPE COMPAGNINI3, LUISA
DURSO3, GIUSEPPE PALLESCHI2, FEDERICA VALENTINI2,
GIANCARLO ANGELINI4 AND TIBOR BRAUN5
1

Lupi Chemical Research, Rome, Italy

Department of Chemistry, Tor Vergata University, Rome, Italy
3
Dipartimento di Scienze Chimiche, Universit di Catania, Catania, Italy
4
CNR, Institute of Chemical Metodologies, Monterotondo Scalo (Rome), Italy
5
Institute of Chemistry, L. Eotvos University, Budapest, Hungary

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Graphene nanoribbons were obtained by oxidative unzipping reaction conducted on

multi-walled carbon nanotubes (MWCNTs). The oxidized and reduced nanoribbons
(after treatment with hydrazine) were characterized by FT-IR and Raman spectroscopy.
Graphite oxide was used as reference material in FT-IR and highly oriented pyrolytic
graphite was used as reference in the Raman study. The transmission electron
microscopy (TEM) of the nanoribbons both in oxidized and reduced form show
beautiful images confirming the single graphene structure of the nanoribbons. When
heated in a thermobalance at 10
C/min under N2, the oxidized nanoribbons undergo an
explosive decomposition at 152
C with formation of a fluffy carbon soot whose FT-IR
spectrum is analogous to that of the hydrazine reduced nanoribbons.
Keywords FT-IR, Graphene nanoribbons, MWCNTs, oxidation, Raman, TEM, thermal
analysis, unzipping reaction

Introduction
The work of Novoselov and colleagues (1,2) on the synthesis of graphene from graphite by
micromechanical cleavage has paved the way on possible applications of a single graphene
layer ranging from next-generation transistors to light-weight, high-strength composite
materials (3,4). Commercial availability of graphene will depend on the development of
an industrially viable method of producing and handling graphene; hence a number of new
articles and patents have been dedicated to new and more practical synthetic routes for the
production of graphene sheets (3,4). The most typical approach in graphene synthesis
involves the oxidation of graphite into graphite oxide (GO) and its reduction and stabilization into exfoliated graphene sheets (36). Examples of other synthetic approaches to
graphene involve the sonochemical exfoliation of graphite intercalated with bromine (7),
the use of an electric arc under determined conditions (8), graphite exfoliation in ionic
liquids (9), epitaxial growth of single layer of graphene sheet for instance on copper surface
(10) using also chemical vapour deposition (11,12) or even bottom-up approach based on the
Address correspondence to Franco Cataldo, Lupi Chemical Research, Via Casilina 1626/A,
00133 Rome, Italy. E-mail: franco.cataldo@fastwebnet.it

261

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F. Cataldo et al.

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use of common laboratory reagents ethanol and sodium followed by thermal decomposition
and sonication (13).
Instead of using graphite or carbon vapor as raw material for graphene, carbon nanotubes were also used as starting substrates to produce graphene nanoribbons (1417).
Similar chemical treatments reserved to graphite were applied to carbon nanotubes. Thus,
the strong oxidation of the nanotubes leads to the unzipping reaction of the rolled-up
graphene sheets producing graphene nanoribbons. Since multi-walled carbon nanotubes
(MWCNTs) are more readily available than the single walled, they were used in the first
studies. Indeed, it has been reported that MWCNTs can be easily unzipped into graphene
sheets and nanoribbons (16) by the action of oxidizing agents like for instance KMnO4 and
concentrated sulphuric acid (17). Beautiful single layer graphene sheets have been detected
by High Resolution Transmission Electron Microscopy (HRTEM) (17).
This article is a confirmation of the results of Kosynkin et al. (17) on graphene
nanoribbons prepared from MWCNTs using an improved synthetic procedure.

Experimental
Materials and Equipment
MWCNTs were obtained from Mitsui (Japan) all the other chemicals from Aldrich, (USA
and Germany).
Raman spectroscopy was performed using the 514.5 nm radiation coming from an Ar
ion laser. Scattered light was collected by an Olympus BX40 optical microscope and
analyzed by a Jobin Yvon single monochromator equipped with a liquid nitrogen cooled
CCD detector. A notch filter for stray light rejection was used. The laser power onto the
sample was limited to 2 mW to avoid heating effects.
FT-IR spectroscopy was made in reflectance mode on samples deposited on a Ge crystal
using a Nicolet spectrometer model IR300 from Thermo-Fisher Corp.
Thermogravimetric analysis was performed on a Linseis apparatus model L81+DTA
under N2 flow (20 L/h) at a heating rate of 10
C/minute.
HRTEM experiments were performed using a TEM Philips (CM120, having LaB6 as
filament) 100kV high-resolution scanning transmission electron microscope. Graphene
sample was previously dispersed in ethanol (1mg/5mL) using an ultrasonic bath for 1h, at
R.T. For TEM investigation, a perforated carbon Formvar film supported by copper grids
(j3mm) was dipped in this graphene dispersion for few seconds. Then, the solvent was
evaporated with the aid of an IR lamp.

Synthesis of Reference Graphite Oxide (GO)

The sample of GO was prepared from micronized graphite (Aldrich) following a synthetic
procedure (18).

Synthesis of Graphite Oxide Nanoribbons from MWCNTs

The GO nanoribbons were prepared by unzipping Mitsui MWCNTs with KMnO4 using an
improved procedure based on that already published (1). The improvement refers to the fact
that almost all small-molecule impurities were removed by repeated washing with aqueous

Characterization of Graphene Nanoribbons from the Unzipping of MWCNTs

263

HCl, ethanol and ether. The content of hydroxyl groups in this material greatly exceeds that
of carboxyls. The ribbons are dispersible in water, 95% ethanol, methanol or DMF.
Reduction of Nanoribbons

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The GO ribbons flakes were reduced with hydrazine as already reported (17). The reduced
graphene flakes were stored as a suspension in 200 ml aqueous solution of hydrazine
(ca. 100 ml of N2H4H2O) in the presence of ammonia (ca. 100 ml of NH4OH). The
concentration of hydrazine and ammonia lead to a pH10. In these conditions the suspension is stable for months provided that a small amount of silicone oil is added to prevent
clumping. The ribbons may irreversibly flocculate on long storage. The only suitable
solvents for the reduced nanoribbons, when isolated as a solid powder, are superacids
such as oleum and chlorosulfonic acid.

Results and Discussion

Spectroscopical Characterization of Nanoribbons Prepared from MWCNTs
The chemical structure of graphite oxide (GO) is quite well known as reported in
several reviews and recent articles (1824). The oxidation causes an expansion of the
interlayer distance of the graphene sheets from 0.335 nm of original graphite to
0.61.1 nm after oxidation (19). The structural models of GO involve the retention
of the graphene layer structure but with a relatively large degree of oxygen content
ranging from C7O4H2 to C24O13H9 with the oxygen groups under the form of keto and
enol groups as well as carboxylic and aldehyde groups, depending on the degree of
oxidation reached. Also epoxide bridges have been reported. More recently detailed
FT-IR and NMR investigations have substantiated the proposed structures (2024).
Thus, the FT-IR spectrum of GO used as reference in the present work shown at the
top of Figure 1, is characterized by a strong OH stretching band at about 3400 cm-1
and by the OH bending at 1226 cm-1. The carbonyl group is a relatively broad band at
1710 cm-1 (with a shoulder at 1755 cm-1) whose intensity exceeds that of the  OH at
3400 cm-1. Ketone groups, carboxylic acids and also aldehyde groups are associated to
this carbonyl group absorption band. In particular the absorption at 1755 cm-1 in
combination with the broad features at 27502850 cm-1 can be assigned to aldehyde
groups which in any case represent by far the minor fraction among the various
oxidized groups in GO (25). Also anhydride groups may be present (18).
The FT-IR spectrum of the GO nanoribbons obtained from MWCNTs (nano-GO) is
visible in the middle of Figure 1 and shows many analogies with the FT-IR spectrum of GO
just described. First of all in the case of nano-GO, the OH absorption band at about 3400
cm-1 is more intense than the carbonyl group absorption and this suggests a higher content of
hydroxyl groups rather than ketone groups as in the case of GO. The sample of nano-GO is
also characterized by a relatively broad ketone band showing two sub-features at 1755 and at
1713 cm-1. The former band in this case has the same intensity of the latter but the broad
absorptions in the range between 2850 and 2750 cm-1 are completely absent in the spectrum
of nano-GO, which is completely free from aldehyde groups. Thus, only ketone and
carboxylic groups are present in nano-GO. The band due to ketone functional groups
conjugated with alkenes or aryl groups appears at higher frequencies in the nano-GO sample
and instead is shifted to lower frequency in the GO sample (1622 versus 1580 cm-1,
respectively). This effect could also be linked to the water content of the sample (19).

264

F. Cataldo et al.

1432

1755

0.6

1708

Abs

0.8

1226

10530 Graphite oxide 1000 scan Ge

1581

1.0

0.4
0.2

0.4

1049

1226

0.6

1411

1755
1713
1622

Abs

0.0
1.0 2836 NANORIBBONS 1000 SCAN Ge
0.8

0.6

804

731

0.8

1091

1586 1560
1502
1403

1.0

1252

0.0
1.2 *2836 nanoribbons reduced 1000 scan Ge

Abs

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0.2

0.4
0.2
3000

2000

1500

1000

800

Wavenumbers (cm1)

Figure 1. FT-IR spectra in reflectance on Ge crystal. Graphite oxide (GO) prepared from the oxidation
of graphite flakes (top), graphene nanoribbons obtained from MWCNT oxidation (nano-GO) (middle)
and in reduced form (red nano-GO) (bottom).

Concerning the C-O bending, the nano-GO sample shows the GO band at 1226 cm-1 but at
considerable lower intensity, accompanied by another band at 1049 cm-1, which suggests
the presence of ether groups (C-O-C) and which is not present in the GO spectrum.
The reduction of the of nano-GO (red nano-GO) with hydrazine treatment is testified by
the complete disappearance of the ketone absorption bands at 1755 and 1713 (see Figure 1,
bottom). Only the absorption band at 1622 cm-1 survived the treatment and appeared shifted
to 15801560 cm-1, at the same absorption position of the analogous band of GO. Even after
reduction with hydrazine the OH absorption band survived the treatment since the bands at
3400, 1252 and 1091 cm-1 are clearly detectable.

Raman Spectroscopy
Raman spectroscopy is a widely used tool for the characterization of carbon products,
especially considering the fact that conjugated and double carbon-carbon bonds lead to
high Raman intensities (26). Highly ordered graphite has only a couple of Raman-active
bands visible in the spectra (Figure 2), the in-phase vibration of the graphite lattice (G band)
at 1575 cm-1 as well as the (very weak) disorder band caused by the graphite edges (D band)
at approximately 1355 cm-1.

Characterization of Graphene Nanoribbons from the Unzipping of MWCNTs

265

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Raman Intensity (a.u.)

Oxidized graphene
Reduced graphene
HOPG

500

1000

1500

2000
2500
Raman Shift (cm1)

3000

3500

Figure 2. Raman spectra of reduced nano-GO (top), and oxidized nano-GO (middle) graphene
nanoribbons compared with the spectrum of an Highly Oriented Pyrolytic Graphite (HOPG) shown
at the bottom of the figure as reference.

While the lattice vibration with the frequency of the D band is, in fact, present in the
infinite graphene sheet, it remains Raman-inactive until the edges light it up due to the
symmetry breaking and the corresponding change in the selection rules. Both the G and the
D bands undergo significant changes upon amorphization of graphite as amorphous carbon
contains a certain fraction of sp3 carbon (27,28) while the presence of sp hybridization is
marked by signals in the region around 2000 cm-1(29,30).
A universal observation is that higher disorder in graphite leads to a broader G band, as
well as to a broad D band of higher relative intensity compared to that of the G band.
Oxidized and reduced graphene transformation leaves behind topological defects and
vacancies such as the well known double vacancy, which is composed of two pentagonal
rings and one octagonal ring and is usually referred to as the 5-8-5 defect (31). For this
reasons the Raman spectra of the two graphene samples shown in Figure 2 undergo changes
that are similar to those observed in the graphite to amorphous carbon transition. Table 1
shows the major ones in terms of D and G lines position and width and ID/IG integrated
intensity ratio. In the Raman spectrum of nano-GO, the G band is broadened and shifted to
with respect to graphite at 1600 cm-1. In addition, the D band at 1363 cm-1 becomes

Table 1
Changes in the Raman spectra of nano-GO
GO-nano

Oxidized

Reduced

oD
(FWHM)D
oG
(FWHM)G
ID/IG

1363 cm-1
127 cm-1
1600 cm-1
86 cm-1
1.4

1357 cm-1
117 cm-1
1601 cm-1
73 cm-1
1.8

266

F. Cataldo et al.

prominent, indicating the reduction in size of the in-plane sp2 domains, possibly due to the
extensive oxidation. The Raman spectrum of the reduced nano-GO also contains both G and
D bands, however, with an increased D/G intensity ratio compared to that in oxidized nanoGO. This change suggests a decrease in the average size of the sp2 domains upon
reduction of the exfoliated GO and can be explained if new graphitic domains were created
that are smaller in size to the ones present in GO before reduction, but more numerous in
number.

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Thermal Analysis of Nano-GO in Comparison to GO

It is well known that under certain circumstances, that is, the heating rate, GO can undergo an
explosive deflagration with formation of an unusual soot with a high specific surface area
(19). In addition, the morphology of such soot when studied at TEM appears similar to a
heap of crumpled paper sheets with dimensions depending on the degree of oxidation of the
employed GO with unusual catalytic activity even for an activated carbon (19).
Surprisingly also the nano-GO, when heated at 10
C/min under N2 has undergone an
explosive deflagration releasing a dark fluffy soot inside the TGA quartz tube which was
cooled and collected. Figure 3 shows the TGA traces of nano-GO in comparison to a normal
GO. The former material has undergone an explosive decomposition at 152
C as indicated
by the vertical weight loss of the TGA, while GO decomposes slowly at the same heating
rate, releasing the volatile fraction of 43.6% and a carbon residue of 56.4%. Such level of
weight loss observed on GO is completely in line with literature data (18,19). On the other
hand, the deflagration of the nano-GO obtained by oxidation of MWCNTs has not been
reported until now. Figure 4 shows the differential thermal analysis (DTA) traces of both
nano-GO and normal GO. Both samples show an initial endothermal transition at about
100
C due to the release of adsorbed and trapped water. The amount of water released is
about 10% in both cases (see Figure 3). On further heating, nano-GO gives a sharp

Figure 3. Thermogravimetric analysis of GO and nano-GO heated 10
C/min under N2. nano-GO
derived from the oxidation of MWCNT undergoes an explosive decomposition at 152
C.

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Characterization of Graphene Nanoribbons from the Unzipping of MWCNTs

267

Figure 4. Differential thermal analysis (DTA) of GO and nano-GO heated 10
C/min under N2.
nano-GO derived from the oxidation of MWCNT undergoes an exothermal decomposition at 152
C.

exothermal transition at 152
C (Figure 4) associated with the deflagration while GO does not
show any other important transition at higher temperatures.
The soot derived from nano-GO explosion was cooled under N2 and collected from the
TGA quartz tube and its FT-IR spectrum was recorded on a Ge crystal in reflectance mode.
The spectrum is shown in Figure 5. Quite surprisingly, the FT-IR spectrum of the soot
derived from the thermal decomposition of nano-GO matches the pattern of the spectrum of
nano-GO reduced by hydrazine and shown for comparison in Figure 5. Since it is known that
the GO deflagration to soot is accompanied by the emission of water, CO and CO2 (19), it is
no real surprise to find out that the soot derived from nano-GO deflagration is in reduced
form. Also in this case, the deflagration has necessarily caused the release of H2O, CO and
CO2 leaving a reduced carbon soot whose FT-IR spectrum is similar to the carbon nanoribbons obtained by the hydrazine reduction of nano-GO.

TEM Images of Nano-GO

The TEM images of the nanoribbons derived from nano-GO are shown in Figures 6
and 7. The images show that the cleavage of the MWCNTs was successful and
although oxidized the sheets show clearly that they are constituted by monolayers or
are just a couple of staked layers. The graphene sheets appear corrugated in some area
and linked to the original MWCNT that in some case was not fully but only partially
unzipped. These images provide clear evidences of the success of the process of
MWCNT unzipping by oxidative cleavage.
The reduction with hydrazine does not improve the morphology of the graphene sheets.
Indeed Figures 8 and 9 show the TEM images of red nano-GO where it is possible to
appreciate again the graphene sheets as a single or staked graphene layers. The sheets do not
appear fully planar but present waviness and crumple up in certain points, but in other zones
it is evident that we are dealing with a single graphene layer.

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F. Cataldo et al.
10736 Soot fm thermal dec GO-nano
1252
1192

1.2

1586

Absorbance

1.0
0.8
0.6
0.4
0.2

734

0.8

802

1255
1200

1560

Absorbance

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1.0

1091
1018

2836 reduced GO-nano

1.2

0.6
0.4
0.2
3500

3000

2500

2000
1500
Wavenumbers (cm1)

1000

Figure 5. FT-IR spectrum (reflectance on Ge): soot formed from thermal decomposition of nano-GO
at 152
C under N2 (top); hydrazine reduced nano-GO (bottom).

Figure 6. TEM image of oxidized graphene nanoribbons (nano-GO) obtained from MWCNT.

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Characterization of Graphene Nanoribbons from the Unzipping of MWCNTs

269

Figure 7. TEM image of oxidized graphene nanoribbons (nano-GO) obtained from MWCNT.

Figure 8. TEM image of reduced graphene nanoribbons (red nano-GO) obtained from MWCNT.

Downloaded by [University of Guelph] at 09:16 09 June 2012

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F. Cataldo et al.

Figure 9. TEM image of reduced graphene nanoribbons (red nano-GO) obtained from MWCNT.

These TEM images are completely analogous to those presented by Kosynkin and
colleagues (17) and confirm their earlier results.

Conclusion
MWCNTs can be used as starting raw materials to produce high quality graphene nanoribbons (nano-GO). The oxidative attack conducted on MWCNTs causes the cleavage of the
tubes and the formation of nano-GO. Both in oxidized and in reduced form the nano-GO
displays beautiful TEM images confirming their single graphene nature. Raman spectroscopy was used to study the nature of the nano-GO. Instead FT-IR spectroscopy was used for
the determination of the functional groups present in the oxidized nanoribbons and to detect
the effectiveness of the reduction after the treatment with hydrazine. The thermal stability of
the nano-GO was checked by TGA and DTA as compared to a sample of graphite oxide
(GO). The sample of GO released gradually all the oxygenated groups by heating without
any sudden decomposition which instead occurred at 152
C in the case of the sample of
nano-GO. The explosive decomposition of the nano-GO was accompanied by the release of
carbon soot in reduced form. Similar phenomena of explosive decomposition of certain
types of GO were reported previously (19).

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