NEW CARBON MATERIALS

Volume 24, Issue 2, June 2009

Online English edition of the Chinese language journal
Cite this article as: New Carbon Materials, 2009, 24(2):147152.

RESEARCH PAPER

In situ synthesis of graphene oxide and its composites

with iron oxide
V. K. Singh, M. K. Patra, M. Manoth, G. S. Gowd, S. R. Vadera, N. Kumar*
Defence Laboratory, Jodhpur-342011, India

Abstract: A single step method was developed for the preparation of graphene oxide/Fe2O3 composites by exfoliation of graphite oxide with an oxygen-rich ferric acetyl acetonate complex. The synthesized materials were characterized by Fourier transform infrared
spectroscopy, X-ray diffraction, vibrating sample magnetometry, atomic force microscopy, and low temperature dc conductivity measurements. After exfoliation, the Fourier transform infrared studies reveal the decomposition of epoxy groups and the simultaneous formation of composites of iron oxide particles within the graphene oxide. Atomic force microscopy reveals the formation of an ~5nm thick
graphene oxide stack with layered morphology. The layered morphology of graphene oxide degrades at higher concentrations of iron
oxide. The vibrating sample magnetometer studies show ferromagnetic behavior of all composites in the range of 0.13-5.5 emu/g at room
temperature. The conductivity of these composites is found to be governed by a quasi 1D hopping mechanism.
Key Words: Graphite Oxide; Graphene oxide; Iron oxide; Composite

Introduction

The graphene, a two dimensional form of carbon, was

first reported in 2004[1] and has generated curiosity among
material scientists to study its properties like very low resistivity, high mobility of charge carriers, and new quantum hall
effect at room temperature[2-3]. The interest also comes from
the presence of various oxygen bearing functional groups
(C=O, CO, OH) in the structure of graphene oxide[4-7],
which can lead to synthesis of various composites of varied
electromagnetic properties[8-9].
Recently, the efforts were made on making ~10 nm thick
layer of graphene on SiC/SiO2 substrate to show extraordinary
properties of ballistic charge transport leading to their potential application in various electronic devices[3, 10-11]. At the
same time, considerable efforts have been made to synthesize
composites of graphene oxide with polymers, metals, and their
alloys in a two step chemical processes[12-21], i.e., initially graphene oxide has been prepared and then re-dispersed in
polymeric solution to tailor electrical and mechanical properties to suit various applications[12], e.g., Lee and Lee have
synthesized graphiteFeSi alloy composites as anode materials for rechargeable lithium batteries[13]. In contrast, Zheng
and Wong prepared poly (methyl methacrylate)
(PMMA)/expanded graphite composites and studied their
electrical properties[14]. It is intriguing that, so far, to the best
of our knowledge, no work has been reported on the synthesis
of composites of graphene oxide with metal oxides.

In the present work, we report insitu formation of iron oxide-graphene oxide composite by exfoliation of graphite oxide
(GO) with ferric acetyl acetonate [Fe (acac) 3]. Interestingly,
structural, morphological, electrical, and magnetic properties
are observed by varying the concentration of ferric acetyl
acetonate.

2
2.1

Experimental
Synthesis of graphene oxide/iron oxide composites

The synthesis of graphite oxide (GO) was carried out by

the following well known Hummers method[22], except for
replacing the step of purification, i.e., dialysis by washing the
product with pre-determined concentration of HNO3. This
modification in the process has not only enhanced oxidation of
graphite but also removes trace impurities of other metal ions.
The product was filtered and thoroughly washed by distilled
water. The golden yellow powder of GO thus obtained was
dried at room temperature for composite preparation. This
dried powder was mixed with solution of different concentrations of Fe(acac)3 in acetone [A1 (9:1 GO/ Fe(acac)3)], A2 (8:2
GO/ Fe (acac)3), A3 (7:3 GO/ Fe(acac) 3), A4 (6:4GO/
Fe(acac)3), and A5 (5:5 GO/Fe(acac)3)], and grinded in a pestle
mortar by allowing the solvent to evaporate leaving behind a
dried precursor composite.
For exfoliation, these precursor composite powders were
taken into round bottom flask covered by thin aluminium foil

Received date: 18 March 2008; Revised date: 28 May 2009

*Corresponding author. E-mail: nkjainjd@yahoo.com
Copyright2009, Institute of Coal Chemistry, Chinese Academy of Sciences. Published by Elsevier Limited. All rights reserved.
DOI: 10.1016/S1872-5805(08)60044-X

V. K. Singh et al. / New Carbon Materials, 2009, 24(2): 147152

Fig.1 (a) FTIR spectra of GO, GO/Fe (acac) 3, and S0. (b) FTIR spectra of graphene oxide/Fe2O3 composites (S1 -S5)

and placed on hot plate. It was observed that exfoliation of

GO/Fe (acac) 3 takes place at ~1500C. The resulting powders
were marked as S1, S2, S3, S4, and S5 for A1, A2, A3, A4, and A5,
respectively. The concentration of iron oxide in composite
materials was estimated by dissolving the powders in conc.
HNO3 and found to be 9.8%, 18.3%, 29.4%, 38.5%, and 47%
for S1, S2, S3, S,4 and S5, respectively. For comparison, a sample of pure graphene oxide was prepared without Fe (acac)3
and named as S0.
2.2

Physical Measurements

The structural characterization of the samples was carried out by powder X-ray diffraction (XRD) performed on a
Philips XPert Pro system by using Cu K1 ( =0.154 060 nm)
radiation. The fourier transform infrared (FTIR) spectra were
recorded in KBr by using FTIR spectrometer Model Shmadzu
DR-8101 A. DC electrical conductivity of these materials was
measured as a function of temperature by four-probe method
using Janis closed cycle refrigerator system and Lake Shore
temperature controller model 331. Imaging of the material was
carried out by using NTMDT Solver PRO Atomic Force
Microscope (AFM) in tapping mode. In order to take images,
samples were initially dispersed in ethanol solution and
spray-coated on a freshly cleaved mica surface by using a fine
atomizer. Room temperature magnetic measurements were
carried out by ADE model EV-5 Vibrating Sample Magnetometer (VSM).

Results and discussion

FTIR spectra of pure GO, GO/ Fe (acac) 3, and S0 are

shown in Fig.1(a). In case of pure GO, absorption peaks appearing at 1 726 cm-1, 1 360 cm-1, and 1 405 cm-1 are because of C=O, CO stretching, and O-H deformation vibration,
respectively. Furthermore, bands at 1 225 cm-1, 1 062 cm-1,
and 986 cm-1 are because of epoxy symmetrical ring deformation, CO stretching mixed with COH bending, and out of
plane wagging of OHO, respectively. In addition, observed
broad absorption band at 3 362 cm-1 and a peak at 1 621 cm-1
correspond to vibrations of the absorbed water molecules[23].
In the sample S0,i.e., on exfoliation of GO, the intensity of

C=O and OH absorption peaks are significantly reduced in

intensity with disappearance of absorption peak characteristic
to epoxy group. In case of composite samples (i.e., S1 -S5)
[ Fig.1(b)], we have observed the similar FTIR spectra like S0,
with additional peaks at 637, 545, and 456 cm-1 attributed to
the presence of - Fe2O3 [24]. Furthermore, in these composites,
a shoulder peak is also observed at 696 cm-1 suggesting the
presence of Fe2O3 [25-26]. The intensity of all peaks attributed
to and Fe2O3 increases gradually with increasing concentration of iron oxides.
In order to understand any initial interaction between
Fe(acac)3 and GO, FTIR spectrum was recorded of a representative sample, i.e., GO mixed with 10% Fe(acac)3 before its
exfoliation [in Fig.1(a)]. It has been observed that, the characteristic peaks of GO because of carbonyl group at 1 726 cm-1
and 1 621 cm-1 because of water are shifted to 1 712 cm-1 and
1 615 cm-1, respectively. The observed shifts are quite significant and suggest some interaction between carbonyl (C=O)
and hydroxyl (-OH) groups of GO and Fe (acac) 3. Such shifts
towards lower wave numbers might be correlated to the existence of hydrogen bonding[27] between GO and Fe (acac) 3
before the exfoliation.
The diagram for the formation of graphene oxide/Iron oxide
composites has been shown in scheme.1.
XRD spectra of composite materials are shown in Fig.2.
Sample (S1) prepared with ~9.8% concentration of Fe2O3
shows diffraction peaks corresponding to (002), (100), (101),
(102), (104), and (110) planes of hexagonal carbon structure,
similar to that of pure graphene oxide (S0) (shown in inset
figure). Furthermore, the higher intensity of the peak because
of (104) plane is found to be high as compared to other peaks,
suggesting planar growth of hexagonal carbon phase. However, in samples prepared with higher concentration of Fe2O3
concentrations (~18.3% -29.4%), i.e., S2 and S3, the intensities
of these peaks corresponding to hexagonal carbon phase
gradually decrease and with further increase in iron oxide
concentrations (beyond ~29.4%) in composites samples S4 and
S5, their intensity almost vanishes with formation of iron oxide in both and Fe2O3 phases. Moreover, in samples S1, S2,
and S3 the peaks of iron oxides could not be observed because

V. K. Singh et al. / New Carbon Materials, 2009, 24(2): 147152

Scheme.1 Scheme for the formation of graphene oxide/ Iron

Oxide composites

Fig.2 XRD spectra of graphene oxide/Fe2O3 composites (S1S5). Inset figure shows XRD of graphene oxide (S0)

Fig.3 AFM images of S0, S1 and S5. Inset figure shows height profile of S0

height profile of graphene oxide layers). Images of samples

(S1and S5) show formation of iron oxide particles embedded
within graphene oxide layers. Interestingly, in case of sample
S1, size of particles (~70 nm) are smaller as compared to those
found in sample S5 (~200 nm). Furthermore, the layered morphology of graphene oxide significantly degrades in sample S5
with the dominance of particles that is consistent with XRD
results as the diffraction peaks of hexagonal carbon phase
diminishes with increase in concentrations of iron oxide in the
composite materials. Although, the phase of spherical particles
can not be arrived from AFM image studies, however, results
from XRD and FTIR studies suggest that they might be iron
oxide particles.
Fig. 4 M-H curves of graphene oxide/Fe2O3 composites (S1S5). Inset fig: Variation of coercivity and saturation values with
respect to percentage of Fe (acac) 3.

of its low concentration. From the above observations, it is

clear that planar growth of hexagonal carbon phase has been
hindered because of the increase in concentration of iron oxide
in the composite materials beyond a limit ~29.4% of Fe2O3.
AFM images of graphene oxide as well as of composites
(S1 and S5) are shown in Fig.3. Image of graphene oxide
shows layered morphology having thickness of 25 nm consisting of each stack thickness ~5 nm (inset figure shows

Field dependent magnetization (M-H curves) of composite materials (S1-S5) is shown in Fig.4. All these samples show
ferromagnetic behavior, even at room temperature, because of
the presence of Fe2O3 phases. Furthermore, coercive field (Hc)
as well as saturation magnetization (Ms) values were found to
increase with increase in Fe2O3 concentration in composites
(Inset figure) with maximum saturation magnetization (Ms)
value of ~ 5.5 emu/g in case of sample S5. The higher value of
MS can be attributed mainly to the formation of bigger Fe2O3
particles as revealed in its AFM images.
Room temperature dc conductivity values () of pure
graphene oxide (S0) and its composites (S1S5) are listed in

V. K. Singh et al. / New Carbon Materials, 2009, 24(2): 147152

1D hopping mechanism [30-31].

Fig.5 ln Vs T plot of pure graphene oxide (S0) and composites (S1 S5). Inset fig: lnW vs ln T plot of pure graphene oxide
(S0) and composites (S1 S5)
Table 1

Conductivity values () at room temperature and

values of pure graphene oxide (S0) and graphene oxide/Fe2O3

composites (S1-S5)
Sample Conductivity

/S cm-1

S0

3.44

0.948

S1

3.210-2

1.120

S2

9.110-3

1.126

S3

3.810-3

1.230

S4

8.810-4

1.540

S5

1.910-3

1.837

Table.1, together with values obtained from their temperature dependence conductivity study curves of lnW vs. lnT
(inset Fig.5) [28]. It is evident from the table that, graphene
oxide (S0) shows two orders higher conductivity than composite material containing lower concentration of iron oxides (S1).
Furthermore, decrease in conductivity values is observed with
increasing the concentration of iron oxide (S2 S5). The decrease in conductivity values might be attributed to reduction
of graphene oxide content as well as progressive destruction
of its layered structure as indicated from their XRD and AFM
studies. From the temperature dependent dc conductivity
measurements, shown in Fig.5, the increase of conductivity
values with that of temperature suggests the semiconducting
behavior[28] both in graphene oxide as well as its composites.
Furthermore, the conductivity mechanism in these materials
has been explained by variable range hopping model (VRH)
(as in case of other nanostructure carbon) [29]. The experimental data have been analyzed by using the following equations:

(T)

= 0 exp (-T0/T)

W = dln /dlnT ,

(1)
(2)

where T0 is the characteristic temperature, represents

dimension of hopping, and W is activation energy. The values
of and are shown in Table.1. The values are found to be
>0.5 in both composites and graphene oxide, suggesting quasi

There are several reports regarding graphite intercalation compounds (GIC) [32-33]. In these compounds, conductivity increases because of charge transfer interaction as the
amount of intercalated particles increases. Furthermore, structure of the host matrix remains unchanged even after insertion
of intercalated particles [33]. However, in present studies, graphene oxide/Fe2O3 composites are different from GIC since
carbon layer loses their planarity because of interaction between functional groups of host matrix (graphene oxide) and
Fe2O3 particles, causing a disruption of the electron system.
Hence, decrease of electrical conductivity has been observed
as the amount of Fe2O3 particles increases in the graphene
oxide matrix.

Conclusions

We have synthesized graphite oxide (GO) by modifying

the Hummers method. It is demonstrated here that exfoliation
of GO with different concentrations of Fe(acac)3 leads to the
formation of light weight flaky graphene oxide/Fe2O3 composites, as confirmed by FTIR and XRD studies. Furthermore,
XRD studies of composites show the formation of and
phases of Fe2O3 and degradation of graphene oxide layered
structure. AFM images show particles of Fe2O3 in graphene
oxide matrix and increase in their size together with degradation in layered structure of graphene oxide as the amount of
Fe2O3 increases. VSM studies indicate the ferromagnetic behavior in all composite samples and increase in magnetization
and coercivity values has been observed with increase in concentration of Fe2O3. Semiconducting behavior of composites
with VRH model for the mechanism of their conductivity is
established from their temperature dependent conductivity
studies.

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