www.advmat.
de
Dispersion of Graphene Sheets in Organic Solvent
Supported by Ionic Interactions
By Yanyu Liang, Dongqing Wu, Xinliang Feng,* and Klaus Müllen*
Graphene, a single-atom-thick sheet of hexagonally arrayed
sp2-bonded carbon atoms, has attracted tremendous attention
from both experimental and theoretical communities in recent
years.[1] The unique electronic properties of graphene sheets with
a specific high surface area hold great promise for potential
applications in fabricating various electronic devices, such as
field-effect transistors,[2] ultrasensitive sensors,[3] transparent
electrodes,[4] and novel nanocomposite materials.[5] With this in
mind, mechanical or chemical exfoliation, epitaxial growth on
silicon carbide or metal surfaces, and chemical reduction of
dispersed graphite oxide (GO) have been developed for preparing
graphene sheets.[6–9] The latter approach, using hydrazine as a
reducing agent, provides stable dispersions of reduced graphite
oxide (RGO) in aqueous solution, in this way leading to
processable graphene sheets in large quantities.[10] Great efforts
have been devoted to disperse graphene sheets in water by
utilizing the electrostatic repulsion of negatively charged
carboxylic or sulfonic groups on the graphene surface,[11,12]
whereas the use of organic solvents, such as dichloromethane,
chloroform, and toluene, as media for dispersion and fabrication
of graphene sheets has been rarely addressed, mainly owing to
their poor solubility and strong aggregation in those solutions.
Very recently, Haddon and coworkers obtained covalently
functionalized GO with long-chain alkylamine via formation of
amides, giving rise to stable dispersions in organic solutions.[13]
However, such a complicated chemical process includes the
presence of toxic SOCl2 and stirring at 120 8C for four days
resulting in a soluble GO derivative with a relatively low yield.
Additionally, such covalent functionalization with random
substitutions on the GO surface engenders structural disruption
of graphene sheets leading to poor electronic properties.
Consequently, there is an urgent need for the development of
a facile and efficient approach to produce large-scale processable
graphene sheets in organic solvents. This would further broaden
the scope of applications, such as graphene-based organic and
polymer composite materials or organic electronics utilizing
graphene sheets as active layers.[14,15]
In this communication, for the first time, we describe a
potentially scalable and environmentally friendly method for the
production of GO and RGO sheets dispersed in chloroform. As
[*] Dr. X. Feng, Prof. K. Müllen, Dr. Y. Liang, Dr. D. Wu
Max Planck Institute for Polymer Research
Ackermannweg 10, 55128 Mainz (Germany)
E-mail: feng@mpip-mainz.mpg.de; muellen@mpip-mainz.mpg.de
Dr. Y. Liang
College of Materials Science and Engineering
Nanjing University of Aeronautics and Astronautics
Nanjing 210016, Nanjing (P. R. China)
DOI: 10.1002/adma.200803160
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COMMUNICATION
demonstrated in Figure 1, GO or RGO with negative charges
(COO
) are firstly mixed with a surfactant, in this case with an
amphiphilic molecule carrying positive charge (NR4þ), at a
concentration higher than its critical micellar concentration in
water. Thereby, the surfactant-supported functionalization of
graphene sheets takes place through ionic interactions.[16] The
hydrophilic head of the surfactant is adsorbed on the surface of
GO or RGO, while its hydrophobic tail is oriented towards the
aqueous phase. Chloroform is then added to the above solution
followed by shaking, so that the GO or RGO are transferred to the
organic phase. Apparently, adsorption of amphiphilic molecules
implies an abundant distribution of NR4þ species on the surface
of these graphene sheets, this preventing aggregation and leading
to stable solutions of GO or RGO in chloroform.
Regarding the above transfer process between two phases, the
balance between the solubility of amphiphilic molecules and the
accessibility of positive charges determining the ionic interac-
tions is a critical factor. Three quaternary ammonium salts,
namely tetradecyltrimethylammonium bromide (TTAB), didode-
cyldimethylammonium bromide (DDAB), and tetradodecylam-
monium bromide (TAB) with 1, 2, and 4 alkyl chains, respectively,
were tested in the same manner (Fig. 2). Apparently, TTAB-
functionalized GO sheets remained in the water phase, whereas
most DDAB-functionalized GO sheets were successfully trans-
ferred to the chloroform solution. This finding indicated that the
better solubility of DDAB in chloroform compared to TTAB was
crucial. In contrast, the use of TAB bearing four alkyl substituents
did not allow an efficient transfer from the water phase. This was
not surprising, since the steric hindrance caused by four alkyl
chains could hamper the corresponding ionic interactions in the
aqueous phase.
Apart from the rational selection of suitable amphiphilic
molecules, other experimental parameters, such as pH value,
weight ratio between graphene sheets and surfactant, solvent, and
reducing agent, all have a critical influence on the transfer
efficiency (Supporting Information). For instance, a pH value
around 9 and a weight ratio between GO and DDAB of around 3:1
were found to be the best conditions. Dichloromethane and
toluene with relatively weak polarity with respect to chloroform
did not allow an efficient transfer process (Supporting Informa-
tion). For the preparation of RGO sheets in water, hydrazine was
commonly used as a reducing reagent of GO sheets, leading to the
elimination of most oxygen-containing functional groups and
partial restoration of a p-electron conjugation within the aromatic
system.[11] As a result, the number of residual carboxylic groups
on these RGO surfaces were rather limited for the sufficient ionic
interactions, and ruled out the solution transfer. As an alternative,
NaBH4 was used to prepare RGO sheets, and by this means the
majority of carboxylic groups were preserved after reduction.[11]
Further optimization indicated that the pH value around 9 and
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Figure 1. Schematic illustration of process for transferring graphene sheets from water to reduced graphene sheets on the surface.
chloroform solutions.
weight ratio between RGO and DDAB of 3:2 were crucial
conditions for the efficient transfer process.
Figure 3 shows a typical atomic force microscopy (AFM) image
of DDAB-functionalized GO on a substrate of newly cleaved
highly oriented pyrolytic graphite (HOPG). The sample was
prepared by drop-casting of the above diluted GO dispersed
chloroform solution (0.05 mg mL
1). Some small sub-
micrometer bare parts with thickness around 1 nm were observed
on the HOPG substrate, which could be attributed to the naked
GO sheet not covered by DDAB surfactant (Supporting
Information). The cross-sectional view of the AFM image
indicated that the average thickness of GO sheets was 1.2 nm,
slightly higher than a common monolayer of GO fabricated from
water solution (1 nm).[11] It was reasonable to assume that a
Figure 2. a) Chemical structure of three quaternary ammonium salts used
in this work. b) Images of GO dispersion in water and chloroform
cosolvents using the surfactant TTAB (left), DDAB (middle), and TAB
(right); parallel experiments were conducted using GO (1 mg mL
1, 0.5 mL
H2O solution), surfactant (0.2 mg mL
1, 0.8 mL H2O solution) and 1 mL
chloroform, pH 9.
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certain content of adsorbed DDAB molecules
onto GO surface resulted in a thicker layer.[17]
As far as we know, this is the first example of a
monolayer GO sheet fabricated on a substrate
from organic solution. Unfortunately, the
casting of diluted RGO-NaBH4 chloroform
solution led to few layers deposited on the
HOPG substrate (not shown), which was
presumably due to the strong aggregation of
These DDAB-functionalized GO and RGO-
NaBH4 sheets were further investigated by
Fourier transform Infrared (FTIR) spectro-
scopy in order to determine the extent of ionic interactions.
Figure 4 shows the FTIR spectra of a thin film cast from
water-soluble GO, DDAB, and DDAB-functionalized GO and
RGO-NaBH4, respectively. The FTIR spectra of water-soluble GO
confirmed the presence of C–O–C (nC–O at 1230 cm
1), C–OH
(nC–OH at 1390 cm
1), and C – – O in carboxylic acid moieties (nC––O
at 1730 cm
1).[18–20] The peak located at 1620 cm
1 could be
ascribed to the skeletal vibration of graphitic domains.[11] For
DDAB-functionalized GO and RGO-NaBH4, the band of
carboxylic acid vibration (nC––O at 1730 cm
1) gradually decreased
in intensity, while two new peaks appeared at 1550 (overlapped by
the broad peak in the range of 1680–1530 cm
1) and 1401 cm
1.
This could be ascribed to the asymmetric (nas) and symmetric (ns)
vibration of the COO
group, respectively.[21] The original NR4þ
Figure 3. Tapping-mode AFM image of DDAB-functionalized GO drop-
cast on HOPG.
Adv. Mater. 2009, 21, 1679–1683
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Figure 4. FTIR spectra of water-soluble GO, DDAB, DDAB-functionalized
GO, and RGO-NaBH4 film deposited on quartz substrate from chloroform
solutions.
asymmetric bending peak of DDAB (1636 cm
1)[22] was shifted to
1669 cm
1 for DDAB-functionalized GO and RGO-NaBH4.
Therefore, it is reasonable to conclude that most of the carboxylic
acid groups in GO and RGO-NaBH4 were functionalized with
quaternary ammonium moieties through ionic interactions.
To monitor the degree of reduction of the GO sheets, UV-vis
spectroscopy and electrical conductivity measurements were
employed. As demonstrated in Figure 5, the thin film of
DDAB-functionalized GO sheets displayed an absorption max-
imum at 235 nm with tailing to 800 nm, consistent with a
water-soluble GO deposited film.[10] In contrast, the thin film
deposited by functionalized RGO-NaBH4 sheets showed a 25 nm
bathochromic shift of the absorption peak concomitant with
significant broadening and tailing in the infrared region,
indicating a p-conjugation partially restored within the graphene
plane. For comparison, the direct reduction of GO sheets by
hydrazine atmosphere (RGO-hydrazine) led to a similar spectrum
but with relatively low absorbance, implying a less efficient
reduction within the graphene sheets on the substrate. The thin
film of RGO-NaBH4 was also reduced under hydrazine atmo-
sphere (RGO-NaBH4-hydrazine), as evidenced by additional 5 nm
bathochromically shifted absorption maximum. Accordingly, the
degree of reduction of graphene sheets follows the order:
GO < RGO-hydrazine < RGO-NaBH4 < RGO-NaBH4-hydrazine.
For the electrical conductivity measurement, a thin film (about
200 nm thickness) of the organic solution-processable graphene
sheets (GO and RGO-NaBH4) was fabricated on a quartz
substrate by spray coating followed by annealing at 120 8C to
remove residual solvents. As expected, the GO film was not
conductive, due to the absence of an extended p-electron
conjugation system, whereas the electrical conductivity of the
fabricated RGO-NaBH4 film was up to 305 S m
1, comparable to
Adv. Mater. 2009, 21, 1679–1683 ß 2009 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
COMMUNICATION
Figure 5. UV-vis spectra of deposited graphene films from chloroform
solutions: GO, RGO-NaBH4, and hydrazine-atmosphere-reduced RGO-
hydrazine and RGO-NaBH4-hydrazine.
polycrystalline graphite (1250 S m
1). Further reduction of the
deposited thin films of GO and RGO-NaBH4 under hydrazine
atmosphere (Supporting Information) led to conductivities of 220
and 350 S m
1, respectively. The different conductivities corre-
sponding to their different degrees of reduction of graphene
sheets were consistent with the UV-vis absorption results
demonstrated above.
Figure 6a illustrated that the RGO-NaBH4 dispersion in
chloroform was freely mixed with a typical fluorescent molecule
of pyrene. In general, the intrinsic fluorescence of pyrene was
ascribed to its excimer emission.[23] However, the completely
quenched emission in the RGO-NaBH4 dispersion indicated an
effective electron or energy transfer between the two components.
This was further supported by the absorption and fluorescence
spectra of the thin film. In Figure 6b, the main absorption peaks
of pyrene mixed with RGO-NaBH4 appeared at 325 and 341 nm,
respectively. The slight red shift of 4 nm in comparison with that
of the pure pyrene film suggested an efficient p-interaction
between pyrene and functionalized graphene sheets. In addition,
the characteristic emission of pyrene at 390 nm was completely
quenched (Fig. 6c), further indicating a strong electronic
interaction at the pyrene/graphene interface. The electron or
energy transfer at the interface between the donor and acceptor
molecules, which in the present case leads to remarkable
fluorescence quenching of the donor, highlights the potential
application of graphene sheets as electron accepting materials in
photovoltaic cells.[24,25]
The high conductivity and high surface area of graphene sheets
further qualify them for applications in composite materials.[14]
As a typical example, the facile processability of DDAB-
functionalized graphene sheets enables the well-blending with
organic platinum compound ethylene-bis(triphenylphosphine)
platinum(0) in chloroform solution. Hence, a new class of
functional composites consisting of graphene sheets and
platinum nanoparticles could be created after a simple thermo-
lysis treatment at 800 8C. Transmission electron microscopy
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Figure 6. a) Images from left to right: 1 mg mL
1 chloroform solution of
RGO-NaBH4þpyrene, pyrene, and of RGO-NaBH4þpyrene, pyrene under
UV light (l ¼ 336 nm). b) Absorption and c) fluorescence (excitation
l ¼ 340 nm) spectra of pyrene and RGO-NaBH4þpyrene films deposited
on quartz substrate from chloroform.
(TEM) characterization disclosed that small-sized Pt nanoparti-
cles with an average diameter of 3.5 nm were homogeneously
distributed inside the graphene sheets (Supporting Information).
This uniformity of the composites with small nanoparticles
dispersions would avoid strong aggregation of graphene sheets
and enable the preservation of their unique electronic properties.
The graphene/Pt was therefore employed as a catalyst for the
electrochemical oxidation of methanol.[26] As expected, graphene/
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Pt presented good catalytic behavior with an onset potential of
0.28 V and a maximum current density of 0.21 mA cm
2
(Supporting Information), comparable to the activity of highly
dispersed Pt nanoparticles anchored on carbon nanotubes.[27]
In summary, we have developed a novel approach towards
large-scale processable graphene sheets in organic solution based
on a transfer process assisted by ionic interactions. For the first
time, smooth monolayer graphene sheets could be easily
fabricated on substrates from organic solution. Such a
noncovalent functionlization preserves the extended aromatic
conjugation of reduced graphene sheets, giving rise to a high
conductivity of cast films. Our work renders it possible to
fabricate graphene-based materials using low-cost and envir-
onmentally friendly processing techniques. This achievement
opens up enormous opportunities to use the unique carbon
nanostructure for graphene-related technological applications,
such as composite materials, micromechanical resonators,
transistors, and energy-storage devices.
Experimental
Graphite flakes were obtained from Sigma–Aldrich. All the chemicals
were of analytical reagent grade, and used without further purification. In a
typical experiment, water-soluble GO was synthesized from natural
graphite flakes by a modified Hummers method (Supporting Information)
[28]. A 0.1 M NaOH solution was added to a 20 mL aqueous solution
(1 mg mL
1) of dispersed GO until a pH value of 9 was reached.
Subsequently, 7.5 mg amphiphile in 3 mL water were sonicated to stimulate
micelle formation, and added to the above GO dispersion resulting in a
brown GO aggregation. When 20 mL chloroform was injected into the
above mixture followed by simple shaking, the GO aggregates could be
redispersed in the organic phase. Hence, large-scale functionalized GO in
chloroform solution were achieved after separation of the water phase. For
the preparation of RGO dispersed chloroform solution, NaBH4 was used
as a reducing agent (RGO-NaBH4). Firstly, 600 mg NaBH4 was added to a
75 mL aqueous GO solution after its pH value was adjusted to 10 with
5 wt% Na2CO3 solution. The mixture was then held at 90 8C for 1 h, until a
black RGO aggregation formed, which could be further redispersed in
water via mild ultrasonic treatment. Remarkably enough, after using the
similar transfer procedure as described above, RGO-NaBH4 dispersion in
chloroform solution was easily obtained. The detailed synthesis of
graphene/Pt composites was described in the Supporting Information.
AFM measurements were conducted using a Nanoscope II Multimode
SPM with an AS-12 (‘‘E’’) scanner operated in tapping mode at room
temperature. FTIR spectra were recorded using a Nicolet 730 FT-IR
spectrometer. Raman spectra were performed from 500 to 2000 cm
1
using a Raman spectrometer (Bruker, RFs 100/S) employing a 15798.3 nm
He–Ne laser beam. UV-vis spectra were measured using a Perkin-Elmer
Lambda 9 spectrometer at room temperature. Fluorescence spectra were
determined on a Spex Fluorolog II (212). Electrical conductivity
measurements were conducted on a Jandel microposition probe equipped
with a Keithley data acquisition system (2700). TEM characterization of
graphene/Pt was performed using a Philips EM 420 electron microscope at
an operating voltage of 120 kV.
Electrochemical measurements were conducted using an EG&G
potentiostat/galvanostat Model 2273 instrument. A conventional cell with
a three-electrode configuration was used throughout this study. Working
electrode was prepared by thin-film electrode method. Briefly, 5 mg
graphene/Pt composite was dispersed in 1 mL 0.05 wt% Nafion solution by
ultrasonication for 30 min. Then, 5 mL dispersion was transferred onto a
mirror-polished glassy carbon electrode. A platinum foil was applied as a
counter electrode with a standard Ag/AgCl electrode as a reference
electrode.
Adv. Mater. 2009, 21, 1679–1683
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Acknowledgements
This work was financially supported by the Max Planck Society through the
program ENERCHEM, National Natural Science Foundation of China (No.
50701023). Y. L. gratefully acknowledges the Alexander von Humboldt
Stiftung for the grant of a research fellowship. We thank N. Tsao for his help
in the preparation of the manuscript. Supporting Information is available
online from Wiley InterScience or from the author.
Received: October 28, 2008
Revised: November 26, 2008
Published online: February 6, 2009
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