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A review of fundamental properties and applications of

polymer–graphene hybrid materials†
Cite this: DOI: 10.1039/c3sm00092c

Alison Y. W. Shama and Shannon M. Notley*b

Published on 05 March 2013 on http://pubs.rsc.org | doi:10.1039/C3SM00092C

Received 10th January 2013
Accepted 21st February 2013
DOI: 10.1039/c3sm00092c
www.rsc.org/softmatter
Graphene research is at the interface of many distinct disciplines of science and physics with the potential
to address the great current global challenges. Effective means for producing industrial scale quantities of
this exciting material are under development. Aqueous based methods are highly attractive due to low
costs and limited environmental impact. Expanding the use of graphene into new applications is
dependent upon the ability to make this unique material compatible with a range of other chemistries,
structures and technologies. Modification of the surface properties of graphene with polymers provides
a facile method for achieving this goal.

Introduction mechanical properties which vary signicantly from the bulk

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graphite form.3,4 These distinctive properties have driven

The properties, production and use of graphene has been an
avid area of research during the past decade. Potential appli-
cations of this research are in elds as diverse as electronics,
energy, water, materials and health.1,2 Graphene is a 2 dimen-
sional form of carbon atoms linked together through sp2
hybridisation in a hexagonal lattice. The interest in this mate-
rial is chiey due to the unique physical, electrical, thermal and
a
Dept of Applied Mathematics, Research School of Physics and Engineering, Australian
National University, Canberra 0200, ACT, Australia
b
Faculty of Life and Social Sciences, Swinburne University of Technology, Hawthorn
3122, VIC, Australia. E-mail: snotley@swin.edu.au; Tel: +61 3 92148635
† Electronic supplementary information (ESI) available. See DOI:
10.1039/c3sm00092c
research into the incorporation of graphene in new
technologies.5
A signicant obstacle to uptake has been the difficulty in
achieving commercial quantities of relatively unmodied gra-
phene. Pristine graphene retains the structural integrity and
hence highly valued properties such as electron mobility which
are predominantly found in the single layered material.6 Flat
surfaces may be modied through epitaxial growth however
complex geometries are not possible using this technique.7
Furthermore, many potential applications rely on using gra-
phene in particulate form. Such applications include water
purication and composite reinforcement.8 With an estimated
potential demand for graphene in excess of 570 t by 2017,9
simple, economic and environmentally friendly methods for the

Alison is a PhD student at the Shannon is an Australian

Australian National University Research Council Future Fellow
in Canberra. Her project at Swinburne University of
involves the production and use Technology. His main research
of graphene in water applica- interest is in understanding the
tions. She is creating novel 3D fundamental interactions per-
geometries of graphene through taining to the stabilisation of
hierarchical self-assembly of particulate suspensions in the
aqueous particulate suspensions presence of polymers. Shannon
of graphene in the presence of has recently extended this area
polymers and surfactants. to involve the production of
novel 2D hybrid materials
incorporating graphene and
other van der Waals bonded solids such as MoS2 and WS2 for
applications in water purication, photocatalysis, plasmonics and
the production of anti-microbial surfaces. He has also worked in
areas such as biopolymers and surfactant self-assembly.

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large scale production of pristine graphene are necessary. In
addition, the creation of hybrid materials which incorporate
graphene and so matter such as functional polymers and
polyelectrolytes can potentially increase this utility. Therefore
techniques which produce graphene and functional derivatives
are highly attractive. This review article discusses solution
processing of graphene as a potential means for large scale
production. The ability to modify and enhance properties using
surfactants and polymers to create novel materials and appli-
cations is further discussed.
Exfoliation techniques
Published on 05 March 2013 on http://pubs.rsc.org | doi:10.1039/C3SM00092C
Aside from solution phase exfoliation using sonication dis-
cussed in this review, the reduction of graphene oxide produced
using the modied Hummers method has been extensively
used to create single layer graphene materials.10–12 The use of
reduced graphene oxide has signicant drawbacks such as a
reduction in electron mobility and a non-at geometry,
although the latter is actually a benet in reinforcing applica-
tions.13 The increase in charge is also useful in compatibilising
with polymers and polyelectrolytes in aqueous systems.
Exfoliation of graphene from graphite in the liquid phase
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without signicant modication can be achieved using both
aqueous and non-aqueous systems. Non-aqueous systems
employ either organic solvents or ionic liquids, while aqueous
systems use surfactants or dispersed polymers to enable exfo-
liation of graphene layers. Liquid phase exfoliation can lead to
relatively unmodied or “pristine” graphene in reasonable
quantities for research purposes and the process is scalable.
Typically, the cohesive energy of liquid phase is matched to the
cohesive energy of graphite which promotes the separation of
graphitic and graphene sheets under shear.14 Practically, this
can be achieved through careful choice of the exfoliating liquid.
A vapour–liquid interfacial tension of approximately 41 mJ m 2
minimises the required energy input to attain effective separa-
tion of sheets beyond the range of the strong van der Waals
forces.14,15 Shearing is most oen imparted by sonicating a
suspension of graphite in liquid using a probe or bath. Organic
solvents as well as ionic liquids with the appropriate surface
tension have been used to disperse graphene. Furthermore,
aqueous solution processing has been demonstrated through
lowering of the interfacial tension of water with appropriate
surfactants and polymers. These are described further in the
following sections.
Non-aqueous systems
Exfoliation using solvents
Exfoliation of defect-free graphene in the liquid phase was rst
demonstrated concurrently using non-aqueous conditions by
Blake et al.16 and Hernandez et al.17 The method reported by
Blake and co-workers was developed as an alternative to the
reduction of graphene oxide and was intended for use in thin,
transparent conducting lms. It involved exfoliating graphene
in the liquid phase via sonication of natural graphite crystals in
dimethylformamide (DMF) and subsequent centrifugation.
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AFM and TEM evidence indicated up to 50% of the resulting
exfoliated akes were monolayer.
Similarly, Hernandez and colleagues prepared dispersions of
graphite powder in a number of organic solvents. N-Methyl-
pyrrolidone (NMP), N,N-dimethylacetamide (DMA), g-butyr-
olactone (GBL) and 1,3-dimethyl-2-imidazolidinone (DMEU)
followed by sonication and mild centrifugation. These organic
solvents were selected primarily because of their use in
dispersing carbon nanotubes in previous studies. As the three
dimensional structure of nanotubes are a derivative of graphene
sheets, it was reasoned that similar interactions occurred
between the solvent and nanotube sidewall, and between the
solvent and graphene. It was shown that the exfoliation of
graphite using NMP resulted in a wide variation in ake thick-
nesses, with approximately 28% of akes appearing as monolayer
graphene and an overall graphene concentration of 1 wt%.
Since these initial reports, a variety of other solvents have
been used to demonstrate the successful exfoliation of gra-
phene in the liquid phase. Hamilton et al.18 demonstrated the
use of ortho-dichlorobenzene (ODCB) in exfoliating graphene
from a range of graphitic materials. Exfoliation of microcrys-
talline synthetic graphite, expanded graphite and HOPG yielded
graphitic concentrations of 0.03 mg mL 1, 0.02 mg mL 1 and
0.02 mg mL 1 in ODCB respectively. However, it was demon-
strated that the use of other aromatic solvents including
benzene, toluene, xylenes, chlorobenzene and pyridine were
unsuccessful in exfoliating graphite.
In addition to organic solvents, ionic liquids have also had
limited use in the exfoliation of graphene.19,20 Concentrations of
0.95 mg L 1 were achieved by Wang et al. when using 1-butyl-3-
methyl-imidazolium bis(triuoro-methane-sulfonyl)imide.
Predominantly the particles were less than 5 sheets in thickness
and up to 1 mm in lateral size. The relatively high cost of this and
other ionic liquids will likely preclude this method for scaling to
industrial quantities.
Aqueous systems
Exfoliation using surfactant solutions
Aqueous solution based processing has signicant advantages
over the use of organic solvents and ionic liquids. These include
much lower costs associated with using water as the liquid
medium as well as fewer potential safety and environmental
issues. In order to achieve the optimum interfacial tension
range for efficient exfoliation, surfactants are added.21–25 As
demonstrated by Fig. 1, practically any surfactant promotes
exfoliation (and summarised in the ESI†).
The surfactant furthermore adsorbs onto the particulate
surface creating an extra repulsive barrier which inhibits re-
aggregation of the sheets. This, however, limits the efficiency of
production using this method as adsorption depletes the
surfactant from solution and hence raises the interfacial
tension beyond the range where exfoliation of graphite into
graphene occurs. Hence strategies which overcome this self-
limiting process have been investigated including continuous
addition of surfactant as schematically shown in Fig. 2.
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Fig. 1 Concentration of graphene in aqueous dispersions, using a range of
different surfactants to facilitate exfoliation. The graphene concentration was
estimated using UV-vis absorption measurements for two initial surfactant
concentrations (0.5% and 1.0% w/v). (Adapted with permission from L. Guardia
et al., Carbon, 2011, 49, 1653–1662, Copyright 2011 Elsevier.)
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Fig. 2 Schematic representation of the production of highly concentrated
suspensions of graphene through surfactant assisted exfoliation with continuous
addition of polymeric surfactant. (Reproduced with permission from S. M. Notley,
Highly concentrated aqueous suspensions of graphene through ultrasonic exfo-
liation with continuous surfactant addition, Langmuir, 2012, 28, 14110–14113.
Copyright 2012 American Chemical Society.)
Following initial studies into graphene exfoliation in
solvents by Blake et al.16 and Hernandez et al.,17 Lotya et al.26
reported the rst sonication-based exfoliation of graphite in an
aqueous system using the cationic surfactant, sodium dodecyl
benzene sulfonate (SDBS). Although the graphene concentra-
tion was maximized for concentrations of SDBS approaching
the CMC, the concentration typically remained low aer
centrifugation, reaching only a maximum of 0.05 mg mL 1.
TEM measurements, as shown in Fig. 3, indicated 45% of
exfoliated graphitic material was less than 5 layers thick, with
only 3% being monolayer graphene, far less than that achiev-
able using solvent exfoliation. Thermogravimetric analysis and
HRTEM measurements also indicated the presence of residual
surfactant. This was cited as the main reason for the relatively
low DC conductivity (35 S m 1) of lms made by vacuum
depositing the obtained graphene.
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Fig. 3 Left: a TEM image of a monolayer graphene flake, exfoliated using SDBS.
Right: a high-resolution TEM image of a surfactant exfoliated monolayer gra-
phene flake. Inset: fast Fourier transform (equivalent to an electron diffraction
pattern) of the image. (Adapted with permission from M. Lotya et al., J. Am. Chem.
Soc., 2009, 131, 3611–3620. Copyright 2013 American Chemical Society.)
Properties and features of solution based exfoliated graphene
The solution based exfoliation method yields graphene with
unique properties and features compared with common wet
chemical techniques, which typically result in graphene oxide
or reduced graphene oxide. The chemical oxidisation of gra-
phene involves breaking the p–p bonds existing between adja-
cent, planar carbon atoms. This not only facilitates exfoliation
of the layers but causes defects in the lattice, converting the sp2
hybridised carbon atoms to sp3 and disrupting the p conjuga-
tion. Although subsequent reduction of the graphene sheets to
form reduced graphene oxide (r-GO) is possible by the use of
reducing agent such as hydrazine, the step is typically incom-
plete and seldom restores the graphene sheets to their pristine
state. Conversely, the graphene lattice is preserved during
liquid phase exfoliation due to the physisorption of stabilisa-
tion species.
The effect of processing on graphene quality is evident when
considering the electrical conductivity of graphene thin lms.
The conductivity of lms prepared using aqueous and non-
aqueous exfoliation methods can reach values as high as 1500 S
m 1 (20 nm thick) and 13 000 S m 1 (8 mm thick) respec-
tively.27,28 This is signicantly different from mechanically
exfoliated monolayer graphene, which is expected to exhibit an
electrical conductivity of 300 000 S m 1.29 However, defects
introduced into the lattice during the oxidation and reduction
of graphene deteriorate the electrical conductivity of the lms
further from the ideal. As a result, reduced graphene oxide lms
exhibit a lower electrical conductivity of approximately 7000 S
m 1, while graphene oxide lms are generally considered non-
conductive.
Liquid phase exfoliated graphene can also be distinguished
from other graphitic materials using Raman scattering. Raman
scattering is a non-destructive technique that reveals the scat-
tering behaviour of phonons with both the electronic and
crystallographic structure of graphene. Although most graphitic
materials scatter phonons in the region 800–2000 cm 1, Raman
scattering is particularly effective in distinguishing ordered and
disordered carbonaceous materials based on the intensity,
wavelength and breadth of three prominent peaks: the D, G and
2D peak (although the position of the peaks are also dependent
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Fig. 4 Raman spectra of (a) pristine natural graphite powder, (b) graphene
dispersion stabilized by the non-ionic surfactant P-123, and (c) chemically reduced
graphene oxide. (Adapted with permission from L. Guardia et al., Carbon, 2011,
49, 1653–1662, Copyright 2011 Elsevier.)
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on the excitation wavelength).30 Typical Raman spectra for
graphite and exfoliated graphene are shown in Fig. 4.
The G peak at 1570 cm 1 appears as a consequence of the in-
plane sp2 carbon structure, and is evident in Raman spectra for
all graphitic materials. For r-GO, the peak is broader than that
observed for graphene.31 The D peak at 1360 cm 1, however
results from the out-of-plane breathing mode of the sp2 carbon
atoms and indicates the proportion of sp3 carbon atoms in a
sample. The peak occurs when defects in the graphene mono-
layers are present, and when the sp3 edges of small akes are
included in the measurement.30 In the case of liquid phase
exfoliated graphene, the intensity of this peak is signicantly
greater than that of graphite powder, as well as mechanically
exfoliated graphene. This is due primarily to the lateral size of
the graphene akes, which are smaller than the area of the laser
used to perform the measurements. As a result, the sp3 carbons
that form the edges of the akes typically contribute to the
measured D peak. The structure of r-GO and graphene oxide
increases the peak absorbance31 due to the presence of oxygen
containing functional groups on the graphene surface. The
peak at approximately 2700 cm 1, is correctly known as the 2D
peak and given the intensity, wavelength and shape of the peak,
provides an indication of the number of stacked graphene
layers. In the case of mechanical or liquid phase exfoliated
graphene, the 2D peak is a single, symmetric peak centered on
2640 cm 1 (ref. 32) with an excitation wavelength of 633 nm.
Increasing the number of stacked graphene layers increases the
breadth of the peaks and shis the peak to between 2600 and
2750 cm 1.
Regardless of the type of process used to exfoliate graphitic
materials in the liquid phase, the resulting akes also demon-
strate a broad variation in lateral size. The ake size is highly
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dependent on the liquid phase process employed in delami-
nating the individual layers from the bulk graphite. In the case
of surfactant stabilized graphene, TEM and AFM measurements
show the resulting lamellar material typically have a lateral size
of between 100–750 nm.26,33–35 However, these akes can be
smaller than 30 nm (ref. 36) and as large as 1 mm (ref. 37)
depending somewhat on the raw graphite material, in addition
to being irregularly shaped. Reduced graphene oxide and gra-
phene oxide akes have similar variation in shape but are
typically larger in size, with akes having a typical area of
between 100 and 300 mm2.38
The size of graphene-based particles has a direct inuence
on their properties. For example, different sizes of graphene
oxide particles have shown to exhibit different levels of cyto-
toxicity.39 As a result, the inability to separate graphene mate-
rials based on size is a clear disadvantage of the technique.
Recently however, size selection of graphene oxide dispersions
has been demonstrated by varying the sonication regime
applied during the exfoliation process40 and through size
exclusion chromatography.41
The presence of ionisable edge groups or defect points can
lead to the development of surface charge in solvents such as
water. Graphene oxide is negatively charged across a broad pH
region, with the zeta potential becoming more negative as the
pH increases, from approximately 20 mV at pH 2 to 45 mV at
pH 11.11 This behaviour is attributed to the presence of
carboxylic acid and phenolic hydroxyl groups on the particle
surface. In the case where surfactants facilitate exfoliation of
graphene, studies have shown the surfactant is adsorbed to the
graphene surface, with zeta potential plateauing with
increasing surfactant concentration.36 When either an anionic26
or cationic surfactant36 is used to facilitate exfoliation, the zeta
potential reects the overall anionic or cationic charge of the
graphene particles imparted by the surfactant, in addition to
the charge imparted by the negatively charged edge groups. In
the case of the anionic surfactant SDBS, the zeta potential
decreases from 30 mV at pH 2, to 70 mV at pH 12, while
CTAB, a cationic surfactant exhibits a decrease in zeta potential
from 5 mV at pH 4 to 30 mV at pH 10 which suggests that even
aer extensive dialysis, specically bound surfactant monomer
molecules are still present.
Stabilisation and dispersion
One of the challenges in graphene utilization, particularly
where solvents with dielectric constant such as water are
prevalent, is the stabilisation of the suspended sheets against
re-aggregation. Effective stabilisation is possible through elec-
trostatic means when using graphene which is heavily oxidised
as described above. Applications involving aqueous solutions
with even moderate salt concentrations can lead to rapid
coagulation in accordance with the well-known DLVO (Derja-
guin–Landau–Verwey–Overbeek) theory.42–44 Indeed, to prevent
unwanted occulation, stabilisation cannot be simply achieved
through charge associated with edges of the particles across a
range of solution conditions. An effective kinetic barrier can
only be attained through basal plane defects leading to a
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decrease in the intrinsically interesting properties of graphene.
Furthermore reduction of the oxidised graphene to regenerate
the bond conjugation diminishes the stability of the
suspension.
Thus, strategies, as outlined in the preceding sections, where
an increase in the particle charge is observed due to the
reversible or irreversible adsorption of so matter such as ionic
surfactants can be exploited. Dilution or dialysis results in the
desorption of surfactant from the particle surface. Whilst this
may be advantageous as the presence of a monomeric surfac-
tant may reduce the utility of the exfoliated graphene sheets, it
also leads to a signicant reduction in the stability of the
suspension. Hence, modifying the particle surface through
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either covalent graing or alternatively, physisorbed macro-
molecules can stabilise these suspensions.
Polyelectrolytes have been routinely exploited in order to
achieve improved suspension stability45–52 and in particular for
aqueous graphene suspensions.36,53,54 Whilst this may increase
the repulsive barrier to aggregation, high ionic strength can still
result in aggregation. An alternative is to introduce an osmotic
repulsive barrier through steric stabilisation of particles.55–57
This can involve the use of non-ionic polymers such as those of
tri-block type PEO-PPO-PEO.14,22 These polymers which are
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amphiphilic may also be used in the production of graphene
using the surfactant assisted exfoliation technique. Therefore,
relatively unmodied stable graphene particulate suspensions
can be conveniently prepared in a one-step procedure.
Potential uses of polymer stabilised
exfoliated graphene
Graphene–polymer thin lm coatings
A number of studies demonstrate the direct use of liquid phase
exfoliated graphene dispersions to create thin lms and spray
coatings. These lms and coatings have potential in optoelec-
tronic device applications as either optically transparent con-
ducting lms or electrode materials.58 With its high optical
transmittance and low conductivity, graphene provides an
attractive alternative to existing transparent conducting lms
materials, the most widely used being indium tin oxide (ITO).
These coatings are oen expensive, chemically unstable and
typically require further processing. Blake et al.16 demonstrated
the performance of transparent conducting lms of graphene
exfoliated with DMF on glass surfaces, as a possible alternative
to ITO. The resultant lm was equivalent to 4–5 layers of gra-
phene had approximately 90% optical transmittance and
possessed a sheet resistance of 5 kU at room temperature. Given
these properties, the lms were seen as acceptable for some
existing applications that used conventional transparent
conductors. Similar proof-of-concept studies were performed by
spray coating graphene exfoliated using NMP.17 In both cases
however, evidence of residual solvent was present on the
surfaces following annealing, suggesting that the cleaning
procedure requires improvement.
When deposited as a thin lm, graphene also shows poten-
tial as electrode material. This is due primarily to its large
specic surface area, which facilitates electron transport along
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Fig. 5 Composite film of poly(vinyl alcohol) and graphene oxide together with
XRD patterns of component materials. (Reproduced with permission from Xu
et al., Carbon, 47, 3538–3543, Copyright 2009 Elsevier.)
the surface of the graphene. This application has been
demonstrated by the production of high-power density gra-
phene electrodes for electrochemical capacitors, from aqueous
based graphene dispersions using scaleable spray coating
techniques.58 Using an aqueous method of graphene exfoliation
reported by Lotya et al.37 a graphene suspension was prepared
and subsequently spray coated onto glass surfaces coated with
ITO. The resulting electrode materials showed unusually high
scan rates during cyclic voltammetry and galvanostatic charge–
discharge experiments, outperforming graphene oxide elec-
trodes. Simple ltration has also been used as a method for the
development of composite lms as shown in Fig. 5 for poly(vinyl
alcohol) and graphene.59
Layer by layer (LBL) processing is another technique that can
be used to create thin lms that incorporate both graphene and
polymers, enhancing the range of properties and functionality
achievable for graphene thin lms. These lms are formed by
sequentially adsorbing two oppositely charged species to a
substrate surface to form a single bi-layer held together through
electrostatic and steric interactions.60–64 The process is then
repeated to build a multilayer, layer by layer. Since each layer
has a self-limiting thickness, another main advantage of this
method is the ability to control the thickness of the lm to a
greater extent compared to spray coating.65,66
The simplicity of the LBL process enables dispersed
graphitic materials such as reduced graphene oxide and
surfactant exfoliated graphene to be used in a range of LBL
processes, from the simple to the complex. For instance, Li et al.
used the LBL technique to layer r-GO with a cationic poly-
electrolyte–poly(diallyldimethylammonium chloride) using
simple dip coating.11 The layer by layer approach has also been
used with r-GO graed with PAA and PAM.67 Following free-
radical polymerisation of the PAA and PAM to the r-GO sheets,
the assembled sheets were further functionalised with oppo-
sitely charged polyelectrolytes, and the LBL technique used to
create graphene-based thin lms. More recently, a method of
creating LBL lms using defect-free graphene has been devel-
oped.35 In this process, PEI was adsorbed to surfactant stabi-
lized graphene to form cationic graphene, with alternating
layers of the charged graphene and PAA being then adsorbed to
the silica substrates. The resulting deposited mass increases
with pH, whilst lm growth becomes linear.
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Stabilised graphene particles in water purication
applications
Liquid phase exfoliated graphene also shows promise as an
alternative to conventional carbonaceous materials such as
activated carbon, which are used to remove contaminants in
water treatment processes. These materials typically remove
pollutants from water via physisorption. As a result, factors
such as surface area and surface interactions affect adsorption
capacity.68 Hence, graphene dispersed in the liquid phase is an
ideal adsorbent, as it has a similar composition to conventional
carbonaceous materials currently used for water remediation. It
also inherently presents a high specic surface area for
adsorption, in addition to providing differing interactions at the
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edges and surfaces of the sheets which may further enable
adsorption of different species.
In the case of graphene, the chemical and structural nature
of the adsorbing species also affects adsorption capacity. For
instance, the removal of heavy metal ions by graphene relies on
the interaction between oxygen containing functional groups
and ions to achieve adsorption. As a result, pristine graphene
has a lower adsorption capacity compared to modied graphene
in the removal of heavy metal ions.69 Unmodied graphene
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however, exhibits a higher adsorption capacity for organic
molecules, especially those compounds containing benzene,
with adsorption of the molecules arising from p–p interactions
occurring at the graphene surface. Consequently, the pristine
graphene produced using liquid phase exfoliation is likely to be
more suited for the removal of organic molecules.
The performance of pristine liquid phase exfoliated gra-
phene as an adsorbent for water contaminants has not been
studied, although the use of other exfoliated graphitic materials
as absorbents has been reported. For instance, graphene
derived from worm-like graphite has been investigated for use
as an absorbent for uoride.70 This type of graphitic material
was prepared by rst synthesising expanded graphite from
natural graphite, using concentrated sulphuric acid and
hydrogen peroxide, then removing the intercalation
compounds via thermal decomposition. The resulting worm-
like graphite was then exfoliated in NMP using ultrasonication
and centrifugation, similar to other liquid phase methods
which exfoliate pristine graphene. From this, graphene was
shown to exhibit adsorption capacity of 35.59 mg g 1 at pH 7.0,
higher than that of a variety of adsorbents including activated
carbon (23.30 mg g 1).
Biocompatibility and cytotoxicity of graphene modied with
polymers
Polymer stabilised graphene as well as surfaces prepared using
such particles have been explored for potential use in biomed-
ical and anti-microbial applications. In the absence of polymers,
there is still no consensus on the biocompatibility or cytotoxicity
of graphene, graphene oxide or reduced graphene oxide with
conicting studies revealing inconsistent results. However,
biocompatibility or alternatively anti-microbial activity of gra-
phene can be imparted through using polymer modication
with materials which have these inherent properties.71
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The interaction of bacteria with graphene–polymer
composite surfaces has been investigated. As discussed previ-
ously, graphene has some residual negative charge through
edge or basal plane defects which conveniently allows the
adsorption of polycations onto the particle surface. Polymers
which contain quaternary ammonium groups display strong
cytotoxicity, particularly toward bacteria. Poly-L-lysine func-
tionalised graphene oxide was used to create anti-microbial
surfaces whilst promoting the proliferation of adipose derived
human stem cells.72 This cationic polyelectrolyte was well-
known to have anti-bacterial activity and in combination with
the graphene surface demonstrated bactericidal action against
the Gram-negative strain E. coli. The overall at conformation or
lamella structure of the modied graphene particles promoted
the attachment of eukaryotic cells. This demonstrates that with
design foresight, polymer functionalised graphene derivatives
have great potential in biomedical applications.
Other anti-microbial polymers have also been used to
enhance the ability of graphene-based particles and surfaces to
produce a cytotoxic response. These include lactoferrin and
chitosan adsorbed to graphene which resulted in a signicant
loss of E. coli cell viability.73 Composite lms of graphene and
polyvinyl-N-carbazole showed cytotoxicity against both Gram-
positive and Gram-negative bacteria.74,75
Whilst cytotoxicity has been the goal of many studies, others
involving graphene and so matter functionalization have tar-
geted the opposite effect, that is, biocompatibility and cell
proliferation. Sun et al. have used graphene stabilised through
covalently attached polyethylene glycol in order to produce a
material with superior biocompatibility. Indeed, these particles
demonstrated selective recognition of lymphoma cells.76 PEG
modied graphene was also recently studied by Liu et al. in
order to probe lowering of toxicity allowing the loading of non-
water soluble drugs on the particle surface.77,78
Graphene–polymer hydrogels and organogels
Hydrogels are so materials incorporating interconnected
polymer chains with a signicant amount of water retained in
the network structure. This is most oen due to the presence
and self-assembly of small gelling molecules which may cova-
lently or physically cross-link the macromolecules. Many
hydrogel systems have been described in the literature
including those involving polyvinyl alcohol, poly-N-iso-
propylacrylamide and block co-polymer surfactants such as
PEO-PPO-PEO. Hydrogels have many potential uses in
biomedical and tissue engineering applications, as an absorp-
tion or release medium as well as sensor technology. Hybrid
materials involving both organic polymers and inorganic
particles such as clays have been studied with the aim to
improve the mechanical properties of the hydrogel.
Recent studies have also focussed on incorporating gra-
phene into hydrogels to create multifunctional materials.79–82
Gelation using graphene is attractive due to the high surface
area to volume ratio of the particles as well as the ability to
engineer three dimensional materials with vastly improved
mechanical properties. Xu et al. demonstrated the ability to
This journal is ª The Royal Society of Chemistry 2013

Review
Fig. 6 Self-healing nature of graphene-based hydrogel, left schematic diagram
of graphene–DNA hydrogel and right, demonstration of self-healing properties.
(Adapted with permission from Y. Xu et al., Three-dimensional self-assembly of
graphene oxide and DNA into multifunctional hydrogels, ACS Nano, 2010, 4,
7358–7362. Copyright 2010 American Chemical Society.)
self-assemble graphene oxide and DNA into a hydrogel with
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high mechanical strength, stability and absorption capacity.83
This hydrogel was also self-healing using a mild heat treatment
as shown in Fig. 6. The biocompatible nature of hybrid hydrogel
materials also makes them attractive in potential drug delivery
or biomedical applications, particularly when combined with
the ability to stimulate release of the bound solvent. A recent
study showed no in vivo cytotoxicity of graphene modied with
Pluronic F127 tri-block co-polymer upon irradiation with near
infrared light.84
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Graphene hybrid hydrogels and organogels have also been
used as a nano-reactor for the production of functionalised
materials with gold nanoparticles. Gold ions were reduced in
situ by the gelling agent tryptophan with the Au nanoparticles
well dispersed. This method showed that multifunctional
organic–inorganic materials can be readily prepared using
simple procedures.85
Perspective
The challenge remains in producing industrial scale quantities
of graphene for all of the potential uses as described above.
Even at the highest concentrations possible using liquid phase
exfoliation, signicant volumes of solvent will be required
which inhibits the uptake of this particular method for gra-
phene production. Some novel strategies which enable effective
particle stabilisation at high solids content will need to be
engineered. The ultra-high surface area of graphene requires
signicant quantities of stabiliser, a factor which will inevitably
inuence the maximum potential concentration of graphene in
a given solvent such as water. Scaling up this technology will
hence not be straightforward. In some sense, the reduction of
graphene oxide allows a way around this problem as the dried
particles are easily re-dispersed in water, the downside is the
modied properties of particles. However, no studies to date
have discussed the potential for re-dispersing polymer stabi-
lised graphene produced using a liquid phase exfoliation
method.
A signicant positive of utilising graphene is the large
surface area to volume ratio which means that only a relatively
low concentration is required for many applications such as
surface modication, composite reinforcement, coatings and
paints or adsorption of ions and organic material. Thus, the
production of these hybrid materials can be performed in situ
with the exfoliation of graphene.
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Whilst current known applications demonstrate the utility of
graphene in many technologies, undoubtedly further possibil-
ities will arise. Polymer stabilised graphene opens up the
potential for further combining with other materials, such as
inorganics and metal particles for making important contri-
butions to addressing the need for alternative energy
approaches. Research is beginning to focus on graphene in the
plasmonic eld, in photovoltaics and photocatalysis.86
Acknowledgements
SN acknowledges nancial support from the Australian
Research Council under the Future Fellowship Scheme.
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