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Direct electro-deposition of graphene from aqueous suspensionsw

Matthias Hilder,*a Bjorn Winther-Jensen,b Dan Li,b Maria Forsythc and
Douglas R. MacFarlanea
Received 20th January 2011, Accepted 4th March 2011
DOI: 10.1039/c1cp20173e
We describe the direct electro-chemical reduction of graphene oxide to graphene from aqueous
suspension by applying reduction voltages exceeding 1.0 to 1.2 V. The conductivity of the
deposition medium is of crucial importance and only values between 425 mS cm1 result in
deposition. Above 25 mS cm1 the suspension de-stabilises while conductivities below 4 mS cm1
do not show a measurable deposition rate. Furthermore, we show that deposition can be
carried out over a wide pH region ranging from 1.5 to 12.5. The electro-deposition process is
characterised in terms of electro-chemical methods including cyclic voltammetry, quartz crystal
microbalance, impedance spectroscopy, constant amperometry and potentiometric titrations,
while the deposits are analysed via Raman spectroscopy, infra-red spectroscopy, X-ray
photoelectron spectroscopy and X-ray diractometry. The determined oxygen contents are similar
to those of chemically reduced graphene oxide, and the conductivity of the deposits was found to
be B20 S cm1.

1. Introduction
Although graphene was only rst isolated in the early 60s,1 the
discovery of Geim et al. in 2004 sparked great interest of this
new member of the carbon family,2 which since then has
become one of the most intensively studied materials in recent
times.35 Graphene is a monolayer of aromatic sp2 hybridised
carbon which forms 2D crystals6,7 and is the building block of
other carbon species. It can, for example, be rolled up into 1D
carbon nanotubes, scrunched into 0D fullerenes or stacked
to form 3D graphite.3,8,9 Its thinness, mechanical strength,
transparency and conductive properties make it a popular
research subject for electro-chemical applications including
sensors,9 electrodes,1012 transistors,6 solar cells13,14 and fuel
cells1517 to name only a few. Graphene is thought to be a
promising candidate to replace the transparent conductor
indium tin oxide since thin layers are both transparent and
conductive. The lack of functional groups makes it chemically
compatible for most composite applications. Additionally,
functionality can be introduced chemically, thus adding specic
reactivity to it. Graphene is also one of the few materials which
can be produced in the form of single atomic sheets,18 which
makes it very useful for fundamental research.
a

Monash University, School of Chemistry, Clayton, Victoria, 3800,

Australia. E-mail: Matthias.hilder@monash.edu;
Tel: +61 3 990 20323
b
Monash University, Materials Science, Clayton, Victoria, 3800,
Australia
c
Deakin University, 221 Burwood Highway, Burwood, Victoria 3125,
Australia
w Electronic supplementary information (ESI) available. See DOI:
10.1039/c1cp20173e

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Although graphene was predicted not to exist for thermodynamic reasons19 in 2004 Geim et al. produced single atomic
layers of honeycomb carbon by mechanical exfoliation of
graphite.2 This method involves peeling o the surface of a
piece of graphite, one layer at a time, using adhesive tape.
Despite the laborious process, the sheets obtained are of very
good quality. Since then other methods have been reported
including thermal desorption of Si from SiC,20,21 chemical
vapour deposition involving hydrocarbons,22,23 unzipping of
carbon nanotubes,24,25 following protocols of organic
synthetic ring condensations,26,27 electron beam irradiation
of polymers,28 arc discharge involving graphite,29 reacting
ethanol with sodium followed by pyrolysis,30 exfoliation of
graphene in organic solvents,31 heat treatment of nano
diamond32 and solid state reactions.33 All of these approaches
have their own advantages and disadvantages, however one of
the simplest is the reduction of graphene oxide.3439 Graphene
oxide is a highly oxidised form of graphene,4042 which
contains polar organic groups including carboxylic acid,
phenol, aldehyde, and epoxide functional groups.43,44 These
make graphene oxide highly hydrophilic so it can easily be
dispersed in aqueous suspensions.
To reduce the non-conductive graphene oxide (GO) to
graphene, various methods have been established including
thermal reduction,45,46 ash reduction,47 enzymatic reduction48
or heating in reducing atmospheres (e.g. ammonia, hydrazine,
hydrogen).49,50 The most common approach however, is
reduction using hydrazine or dimethylhydrazine from an
aqueous suspension.49,5156 Although hydrazine and its
derivatives are highly toxic, carcinogenic and explosive, it is
one of the few reducing reagents compatible with water.
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More traditional reducing agents including NaN3, NaBH4,

NaH2, etc. can be used in organic media,5759 however in order
to suspend GO in organic solvents it has to be chemically
modied.
Despite the vast amount of information published in recent
years, there has surprisingly been little progress in making
graphene electro-chemically. This is potentially the simplest
and least expensive method, and it is suitable for mass
production, even for large area applications. In principle,
highly controllable, conformal lms can be formed without
the need for volatile solvents or reducing agents. The few
publications on electro-chemically reduced graphene involve
either pre-applying GO dispersions directly onto electrodes
followed by reduction in an electrolyte,6063 functionalising the
electrodes in order to add templating properties to GO64,65 or
chemically functionalising GO and carrying out the deposition
process from organic solvents.66 Electro-depositing from
aqueous suspension rather than post-reducing a preapplied coating of graphene oxide electrochemically would
simplify the process and make graphene materials more readily
accessible for new applications and devices. Here we describe
for the rst time, the direct electro-chemical reduction of
graphene oxide from an aqueous suspension to form thin
lms on the electrode surface, through the control of the ionic
conductivity of the electrolyte mixture. We also discuss the
completeness of the reduction process and compare it to
graphene obtained from reducing GO pre-applied to the
electrode. The products are characterised via infra-red
spectroscopy, Raman spectroscopy, X-ray diraction, X-ray
photoelectron spectroscopy, impedance spectroscopy and
surface charge titration.

2. Experimental
Graphene oxide
Graphite oxide was synthesized from natural graphite
(SP-1, Bay Carbon) by a modied Hummers method as
originally presented by Kovtyukhova and colleagues.42,67
As-synthesized graphite oxide was then puried by dialysis
and then subjected to ultra-sonication protocols which are
described in detail elsewhere.39

with a magnetic stirrer and nitrogen was bubbled through the

medium. A pre-reduction step (5 min, 0.8 V) was introduced
to oxidise the dissolved oxygen.
Constant potential deposition was carried out applying
voltages of 1.0 to 1.4 V. An aqueous GO suspension
(0.5 mg mL1) was mixed 1 : 1 with the NaCl electrolyte
(0.25 M for the pH experiments and varying concentrations
to determine the conductivity thresholds). The pH was
adjusted to values described in the Experimental section using
diluted solutions of sodium hydroxide or hydrochloric acid. The
depositions were carried out for 15 min. Black spongy deposits
with high water contents were obtained. Upon drying at room
temperature, a grey shiny conductive lm was formed. For the
XPS study, these lms were immersed into a GO-free NaCl0.25M
electrolyte for post-reduction (1.0 to 1.4 V). GO suspension
was also cast straight onto the working electrode and posttreated under the same conditions as described above.
To determine the conductivity of the deposit, a glass slide
was plasma cleaned and sputtered with gold (SPI Module
Sputter Coater) leaving a 1 mm gap. Onto this glass strip
graphene oxide was cast connecting the two gold-coated areas.
The GO was electro-chemically reduced (1.2 V, NaCl0.25M).
After drying the thickness was determined using a VEECO
Dektak150 to be B1.0 mm. Then the two gold areas were
electrically connected and the resistivity was measured by
impedance methods (1 Hz to 1 MHz, 3 measurements per
frequency). The surface conductivity was calculated from the
resistivity, the area and the thickness.
A QCM200 Quartz Crystal Microbalance combined with a
QCM25 5 MHz Crystal Oscillator was used for the QCM
experiments. The QCM was used in the same manner as like
the working electrode.
Conductivities of the GO/NaCl suspensions were also
determined by impedance methods (1 Hz to 5 MHz,
3 measurements per frequency). A two platinum electrode
setup was used and the results were calibrated against a KCl
standard solution of known concentration and conductivity in
order to determine the cell constant.
The deposition rates were determined by measuring the
weight of the deposit after 1 h. Using Faradayss law the
molecular weight was calculated from the time, the weight,
the current and the faraday constant assuming a one electroreduction process.

Reagents
Reagents were either used to act as electrolytes or to adjust the
pH and were sodium chloride (Merck, p.a.), potassium
chloride (Merck, p.a.), sodium hydroxide (Merck, p.a.) and
hydrochloric acid (UNIVAR, analytical reagent).
Electro-chemical techniques
All depositions and electro-chemical characterisations were
carried out using a multi-channel potentiostat and controlled
using VMP2 EC-lab 9.56 software. CVs were recorded in the
range of 1.6 V to +1.0 V using a scan speed of 0.1 V min1.
The CV as well as the deposition experiments were carried out
using a three electrode setup including a calomel reference
electrode, a titanium mesh counter electrode and a gold mylar
or glassy carbon working electrode. The solution was stirred
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Phys. Chem. Chem. Phys., 2011, 13, 91879193

IR
IR samples were recorded using a Perkin Elmer Spectrum
RX1 FT-IR spectrometer. KBr pellets were made by grinding
the samples with dried potassium bromide (Merck, p.a.) and
applying the equivalent of 10 tons pressure for 15 min while
applying vacuum. The samples were then spectroscopically
characterised in the region of 500 to 4000 cm1 (16 scans, 4 cm1).
The background was manually removed and the intensity
normalised against the intensity of the CQC stretching
vibration.
XRD
Powder X-ray diractograms were collected using a Philips
PW1130 equipped with a Cu cathode ray tube PW2213/20
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(60 kV, 1500 W) which generated CuKa radiation. A 2y angle

range of 21 to 501 was measured (step width = 0.021, scan
speed of 11 per minute).

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XPS
XPS analysis was performed using an AXIS-HSi spectrometer
(Kratos Analytical Inc., Manchester, UK) with a monochromated Al Ka source at a power of 144 W (12 kV  12 mA), a
hemispherical analyser operating in the xed analyser transmission mode and the standard aperture (1 mm  0.5 mm).
The total pressure in the main vacuum chamber during
analysis was of the order of 108 mbar. A magnetic immersion
lens was used for charge compensation (typically 1 to 4 eV).
The area of analysis is estimated to be 0.35 mm2. A pass energy
of 320 eV was chosen for survey spectra (range 5 to 1100 eV)
while 40 eV was used for high resolution C1s spectra (292277 eV).
The data were analysed using CasaXPS software. The spectra
were corrected using the Shirley approach and the sensitivity
factors supplied by the manufacturer were used for identication.
The position was calibrated against the C1s peak of graphene
which is expected to occur at 284.4 eV.
Raman
A Renishaw Invia Raman Confocal Microscope was used to
study the deposits. The excitation source was a 632.8 nm
HeNe laser system. The excitation energy was set to 50%
and a scan rate of 10 cm1 s1 was chosen. The signal position
was calibrated against silicone.
Micrographs
A Nikon Eclipse ME600 was used to record micrographs of
the lms.

3. Results and discussion

Electro-chemical characterisation of the electro-deposition
process and the deposits
Successful electro-reduction of graphene oxide (GO) to
graphene from aqueous suspension was observed if a reduction
potential of 1.2 V was applied to a neutral GO suspension
(0.5 mg mL1) which was mixed 1 : 1 with a sodium chloride
solution (NaCl = 0.25 M). Fig. 1 shows the cyclic voltammogram
(CV) of the GO dispersion compared to the NaCl electrolyte
alone. The additional reduction current in the region of 1.0 V
to 1.2 V indicates the reduction of GO.
A quartz crystal microbalance (QCM) was also employed to
monitor the electro-reduction process. The inset in Fig. 1
shows the frequency plot as a function of the deposition time.
The frequency dip indicates graphene deposition. Although it
is, in principle, possible to determine the deposited mass from
QCM experiments, the spongy graphene deposits contain
entrapped water (up to 95%) and thus a meaningful direct
measure of mass proved not to be possible.
Experiments showed that adding a supporting electrolyte to
the GO suspension is essential for electro-deposition. An
excess of reagent (acids, bases or salts), however, results in
destabilisation of the suspended GO particles. Graphene oxide
contains anionic functional groups (e.g. phenolates and
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Fig. 1 Cyclic voltammogram of (i) the NaCl electrolyte and (ii) the
GO/NaCl system (working electrode area = 1.5 cm2, scan rate =
10 mV s1), GO starts to reduce at potentials below 1.0 V which is
before the NaCl electrolyte itself begins to reduce. The inset shows the
drop in frequency of an oscillating quartz microbalance electrode
indicating deposition of graphene oxide onto the oscillating quartz
crystal. Reference electrode = saturated calomel electrode.

carboxylates); partial dissociation of these groups results in

negative charges bound to the particle surface. In suspension
these surface charges are responsible for the formation of an
electro-chemical double layer which surrounds the particles.
This layer stabilises the suspended particles by physically
preventing them to agglomerate. The thickness of the double
layer decreases with increasing electrolyte concentration,
hence stabilisation can only be achieved in very dilute systems.
By adding NaCl solutions of varying concentrations to the GO
suspensions (0.5 mg mL1), the quality of the suspension was
evaluated visually and correlated to the overall conductivity of
the medium at pH 7, using impedance spectroscopy. The
threshold conductivity regarding the stability of the GO
suspension was found to be 25 mS cm1. Suspensions of
higher conductivity de-stabilise, forming lumpy agglomerates.
The same approach was adopted to determine the lower
conductivity threshold for electro-reduction of the GO. By
adding NaCl solutions of various concentrations to GO0.5mg mL1
suspension (pH 7) the threshold conductivity for electrodeposition was determined to be 4 mS cm1 or higher if a
reduction potential of 1.2 V was applied. Combining these
two ndings means that there is an optimum conductivity
range between 4 and 25 mS cm1 in which (i) the GO
suspensions are stable and (ii) graphene can be electro-deposited
from aqueous suspensions. It should be mentioned that for
conductivities larger than 25 mS cm1 deposition is still
observed, but the non-uniform nature of the destabilised
suspension results in poor quality lms. Fig. 2a summarises
these ndings.
Another important parameter is the pH of the deposition
medium since it strongly inuences the state of protonation/
deprotonation of functional groups on the GO surface and
therefore inuences both the dispersion stability and the
electro-chemical properties. To study the pH range under
which GO can be electro-chemically reduced, the NaCl0.25M
electrolyte was added to GO0.5mg mL1 suspensions (1 : 1 by
volume) followed by pH adjustment with dilute HCl or NaOH
solutions. The addition of NaCl ensured that the suspension
remained within the optimum conductivity range for electrodeposition (as established above). The CVs for GO/NaCl
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suspensions, graphene deposits at slightly higher potentials for

neutral suspensions (Fig. S3 in ESIw).
At pH 7, the deposition rate was determined gravimetrically
to be 1 mg h1 under the conditions used here. The average
current was 0.52 mA over this time and using Faradays law it
can be estimated that one electron is consumed for every 4
carbons deposited (or equivalently one two-electron reduction
for every 8 carbons deposited). This is in accord with the
degree of oxidation of GO reported.6769
The grey/black colour of the deposit suggests that graphene
oxide (brown) has been electro-chemically reduced to graphene
(black). To determine the conductivity of the deposited lm,
impedance measurements were conducted on the samples over
a 1 mm gap between two gold electrodes. The resistance was
43 O and, with an average thickness of 1.0 mm as determined
by prolometry, the bulk conductivity was calculated to be
23  5 S cm1. The review comparing conductivities of
graphene materials by Park and Ruo reports values ranging
from 2 to 7200 S cm1.70 The present conductivity is therefore
in reasonable accord with these results, though it is important
to note that the surface of the deposit is quite rough and that
an average thickness was used in the calculation. The
determined result is therefore probably an underestimate of
the conductivity of the bulk material.
Fig. 2 (a) After adding NaCl (concentration gradient) to an aqueous
GO suspension (0.5 mg mL1) the pH was adjusted to 7. Then the
stability of the suspension was evaluated visually and deposition
experiments were carried out (1.2 V, Ti counter electrode, calomel
reference electrode) and the gold mylar working electrode was visually
examined for deposits. The conductivity of the suspensions was
determined by impedance measurements (1 Hz to 1 MHz,) at room
temperature (calibrated against a KCl standard solution). There is an
optimum conductivity range between 4 and 25 mS cm1. (b) Deposition
behaviour of GO (0.5 mg mL1) and NaCl (0.25 M) at dierent
pH values. The conductivity for all samples was in the range of
optimum conductivity regarding deposition and stability. Deposits
were obtained in the pH range from 1.5 to 12.5 (1.2 V, calomel
reference electrode, Ti counter electrode).

dispersions at dierent pH values are presented in the ESIw

(Fig. S2). The working electrode was visually inspected for the
presence of deposits after applying a reduction potential of
1.2 V. Indeed it is possible to deposit graphene over a wide
pH range starting from pH 1.5 to 12.5 (see Fig. 2b). Beyond
those pH ranges (pH o 1.5; pH > 12.5) the conductivity
exceeds 25 mS cm1 and the suspension destabilises due to
agglomerate formation. Besides compatibility issues at low pH
(applying a reduction potential of 1.2 V, the gold mylar
substrate disintegrated at pH 1.0) there are also side-reactions
competing with GO reduction. Not only does reduction of H+
compete with GO reduction electro-chemically, but the
formation of hydrogen bubbles also create a physical barrier
which hinders the GO particles to approach the working
electrode, thus interfering with the process. The CVs in the
basic region were similar to those from the neutral region thus
there are no interfering side-reactions and the limitation at
high pH is thought to be caused by compatibility issues. While
electro-deposition is observed at 1.0 V for basic and acidic
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Spectroscopic characterisation of the deposits

Raman spectroscopy has been widely used in the characterisation
of graphene and there are several reviews available.71,72 The
spectrum of graphene oxide and of the electro-deposited
sample is shown in Fig. 3. The Raman spectrum of graphene
usually consists of three main components, the D (A1g) band
which occurs between 1330 to 1360 cm1, the G band (E2g) at
around 1580 cm1 and the G 0 band (2nd order, two phonon
mode) at 2700 cm1. The D peak, which does not occur in
bulk graphite, indicates a decrease in symmetry due to the
defects on the edges. The intensity of the D and G peaks is
reversed once graphene oxide is reduced to graphene. The D
band reects the amount of defects present and it has been

Fig. 3 Raman spectrum of graphene electro-deposited from neutral

suspension at 1.2 V vs. SCE. The intensity changes in the G and D
bands indicate the formation of graphene. The double peak of the G 0
band indicates the presence of bulk graphene (e.g. several layers). The
spectra were obtained by excitation of the sample with a HeNe laser
(632.8 nm, 50% intensity).

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Fig. 4 IR spectra of graphene oxide and graphene electro-deposited

at pH 7.0 at 1.2 V. Although oxygen containing groups are
still present, their concentration is signicantly decreased. This is
particularly true for the presence of groups containing CO single
bonds.

Fig. 5 C1s XPS spectra of graphene electro-deposited from suspension (15 min, 1.2 V) and post-treated in NaCl (15 min, 1.2 V),
compared with graphene oxide applied and post-treated in NaCl
(15 min, 1.2 V). The amount of highly oxidised carbon species
decreases after reduction.

observed by others that the defect concentration is increased in

graphene.63 The reversal is a good indication of the change
that occurred during electro-reduction. The ESIw shows the
diagrams for the deposits obtained at various pH values
(Fig. S4).
Infra-red spectra (IR) of GO and electro-deposited
graphene are presented in Fig. 4. As discussed previously,
graphene oxide contains various oxygen containing functional
groups including ether, epoxide, carboxylic acid, phenolate
and aldehyde groups. The IR indicates the presence of OH,
CH, CQC, CQO and CO groups in GO. The most
dramatic change on reduction occurs in the region of the
CO stretching vibration. After reduction, the signals in this
region are much less intense and less complex compared to the
GO starting material. The same is true for the CQO region.
Reduction thus seems to eliminate mainly CO groups (ethers,
epoxides, esters, carboxylic acids and alcohols/phenols). There
are, however, oxygen containing groups still present even after
reduction. These ndings are in close agreement with the work
of Zangmeister.68
X-Ray diractograms (XRD) were recorded for graphene
oxide and the electro-reduced deposits. While GO has a sharp
diraction signal at 10.81 (d = 0.82 nm) which is associated
with stacking in the (0 0 2) direction, the signal disappears
upon electro-reduction (Fig. S5 in the ESIw). Although this is
of little diagnostic value, the change still indicates that the GO
precursor has been electro-chemically converted.
As discussed above the IR of the deposited graphene lms
indicated the presence of oxidised carbon species. It was thus of
interest to quantify the degree of reduction. To do so, various
treated lms were prepared and investigated by X-ray photoelectron spectroscopy (XPS). Films were deposited by applying
1.2 V for 15 minutes to an aqueous suspension of graphene
oxide (0.5 mg mL1, pH 7.0). The lms were then post-treated by
immersion in a GO-free solution of NaCl (0.25 M) and applying
a reduction potential of 1.0 V, 1.2 V or 1.4 V for 15 min. To
compare the quality of products electro-deposited from aqueous
suspension to previously described reductive techniques,6063
graphene oxide suspensions (15 mg mL1) were cast directly
onto the working electrode and post-treated in an identical

manner (15 min at 1.0, 1.2 and 1.4 V in 0.25 M NaCl).

Fig. 5 shows the C1s XPS spectra of the graphene oxide
(applied and post-treated) and graphene deposits from suspension (deposited and post-treated) and Fig. 6 shows an example
of a C1s XPS spectrum of graphene oxide and a deposited
graphene lm, including curve ts for the various carbon
components. It is evident that graphene oxide shows strong
signals due to the presence of oxidised carbon species
(CO, CQO and OCQO). Upon electro-chemical reduction,
the intensity of these signals decreases. Table 1 shows the

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Fig. 6 C1s XPS spectrum including curve ts for the individual

components of (a) graphene oxide and (b) electro-deposited graphene.

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Table 1 C : O ratios for various graphene electro-deposits derived

from XPS. First graphene was deposited from aqueous suspension
(GO0.5mg mL1, 1.2 V, 15 min). After drying the samples were posttreated in NaCl0.25M for 15 min applying 1.0 V, 1.2 V or 1.4 V.
This method was compared to GO which was cast onto the working
electrode and post-treated using the same conditions. From the survey
spectra the C/O ratio was determined. The results from the survey
spectra were compared to the C/O ratios derived from the C1s spectra.
Components occurring in the range of 284285 eV were assigned to
reduced carbon species while components of higher binding energy
were assigned to oxidised carbon species. The C/O ratios of the two
approaches follow a similar trend
XPS survey

C1s

Electro-deposited Cast Electro-deposited Cast

GO
Initial deposition
1.0 V
1.2 V
1.4 V

3.3
5.1
6.3
6.8
7.8

3.3
NA
5.3
6.5
6.9

2.5
3.5
4.9
4.7
5.9

2.5
NA
3.6
3.6
4.7

C : O ratios derived from the XPS survey spectra and from

the C1s spectra. This shows that the C : O ratios increase with
increasingly negative reducing potentials indicating a decrease
in the oxygen content. The trends from the survey spectra are
in agreement with the results obtained from the C1s spectra.
Dierences result from the assumption that each oxygen atom
is bound to one carbon atom while in reality the oxygen might
be shared between two carbons (e.g. in ether COC bonds)
while other carbon atoms are bound to more than one
oxygen (e.g. CO2 ester or carboxylic acid bonds). The lms
electro-deposited from suspension contain less oxygen
compared to those obtained by reducing pre-applied graphene
oxide. Table 2 monitors the change of various functional
groups during the reduction process. The most signicant
change is observed in the concentration of CO groups
(phenol, ether) which signicantly decreases as the reduction
process proceeds. Although it is possible to remove all oxygen
by for example heating it for 12 hours at 800 1C in a H2/Ar
stream (20% H2, 50 cm3 min1),73 our ndings are in
agreement with reported C : O ratios ranging from 3.6 to
6.4 for chemically reduced graphene oxide employing
hydrazine.6769,73 The observation that the reduction process
mostly aects CO single bond groups is in agreement with the
IR results.

Table 2 Carbon components in the graphene lms based on

components observed in the XPS C1s spectrum. The C1s spectra were
composed of reduced carbon species (e.g. 284285.5 eV), carbon
single bond species (286287 eV) and carbon double bond species
(around 288 eV). Electro-reduction seems mostly to eliminate CO
components
GO
Electro-deposited
1.00
Creduced
CO
0.57
CQO
0.09
Cast
1.00
Creduced
CO
0.57
CQO
0.09

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Initial deposition

1.0 V

1.2 V

1.4 V

1.00
0.30
0.09

1.00
0.15
0.11

1.00
0.16
0.11

1.00
0.16
0.04

NA
NA
NA

1.00
0.21
0.18

1.00
0.21
0.18

1.00
0.20
0.07

Phys. Chem. Chem. Phys., 2011, 13, 91879193

4. Conclusions
Graphene lms have been successfully produced by electrochemical reduction of graphene oxide from aqueous
suspension. A critical parameter in the formation of good
quality lms is the conductivity of the medium; the optimum
conductivity range for the system studied (GO = 0.5 mg mL1)
was found to be between 4 and 25 mS cm1. Below 4 mS cm1
no graphene can be electro-deposited and above 25 mS cm1
the GO suspension becomes unstable. Although these results
are dependent on the system (concentration, history of the GO
sample, electrolyte, etc.) the overall concept of electro-deposition
and suspension destabilisation still applies to all samples. The
electro-deposition can be carried out over the wide pH range
from 1.5 to 12.5. Beyond those pH limits the suspension
destabilises. While in the acidic region H+ reduction competes
with GO reduction, no interfering chemical processes are
occurring in the neutral and basic regions. Deposits were
obtained at 1.0 V for acidic and basic suspensions and at
1.2 V for neutral suspensions. The deposition current at a
given potential was approximately constant over time and the
deposition rate was gravimetrically determined at B1 mg h1
at 1.2 V. Thus lm thickness control could easily be achieved
over a wide range via choice of deposition time. The conductivity
of the lms was of the order of 20 S cm1. While XRD and
Raman indicated that a chemical and structural change occurs
during the electro-chemical conversion, IR and XPS conrm
that the content of CO groups is signicantly reduced upon
electro-deposition. The oxygen content is lower for samples
deposited straight from suspension compared to GO which
was cast onto electrodes followed by reduction in the electrolyte. The oxygen content decreases with increasingly negative
reduction potential.

Acknowledgements
We would like to thank the Australian Centre of Excellence
for Electromaterials Science for funding. DRM and BWJ are
grateful to the Australian Research Council for Fellowships.
We would also like to thank Dr Noel Clark (Commonwealth
Scientic and Industrial Research Organisation) for his input.

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