24 April 1998

Chemical Physics Letters 287 Ž1998. 53–56

A new structural model for graphite oxide

Heyong He a , Jacek Klinowski a,)
, Michael Forster b, Anton Lerf b

a
Department of Chemistry, UniÕersity of Cambridge, Lensfield Road, Cambridge CB2 1EW, UK
b
¨ Tieftemperaturforschung, Bayerische Akademie der Wissenschaften, Walther-Meissner-Strab e 8, D-85748
Walther-Meissner-Institut fur
Garching, Germany
Received 12 January 1998; in final form 2 February 1998

Abstract

Solid-state 13C NMR spectra of graphite oxide ŽGO. and its derivatives prompt us to propose a new structural model. The
spectra of GO treated with KI and the course of the thermal decomposition of GO reveal the presence of epoxide groups,
responsible for the oxidating nature of the material. GO is built of aromatic ‘‘islands’’ of variable size which have not been
oxidized, and are separated from each other by aliphatic 6-membered rings containing C–OH, epoxide groups and double
bonds. The carbon grid is nearly flat; a small degree of warping is caused by the carbons attached to OH groups, which are
in a slightly distorted tetrahedral configuration. q 1998 Elsevier Science B.V. All rights reserved.

Graphite oxide is prepared by treating graphite
with strong aqueous oxidizing agents such as fuming
nitric acidrpotassium chlorate or sulphuric
acidrpotassium permanganate. But, although its was
first prepared in the mid-19th century w1,2x, the
precise structure of GO is still uncertain: because of
its nearly amorphous nature, diffraction methods w3–
6x are of limited use. The various structural models
proposed over the years w3,4,6–9x assume the pres-
ence in GO of various oxygen-containing functional
groups. Most recently GO has been used as the
positive electrode in primary lithium cells w10x, for
the preparation of membranes and as a model system
for membrane states w11–13x, and for the manufac-
ture of novel composites in which GO is reduced to
graphite w14x. It is highly desirable to be able to
)
Correponding author. Fax: q44-1223-336-362; e-mail:
jk18@cam.ac.uk
construct three-dimensional carbon networks by in-
terlinking the GO layers, and modified graphite for
batteries by intercalating and graphitizing GO. The
structure of GO, especially the nature of the func-
tional groups, is therefore of considerable interest. In
particular, the presence of epoxide functional groups
would make GO a very convenient starting material
for many chemical reactions.
Mermoux et al. w15x interpreted their solid-state
NMR spectra of GO with reference to Ruess’s model
w4x, where the carbon grid is in chair-like conforma-
tion and 1,3-ether and C–OH functional groups are
present. They assigned the 13 C lines at 60 and 70
ppm to C–O–C and C–OH groups, and the line at
130 ppm to double-bonded carbon atoms, postulating
that some of the latter are isolated w8x. However,
even this most recent model is not satisfactory. Is it
certain that the C–O–C groups are 1,3-ethers? How
are the C–O–C and C–OH groups, and double
bonds distributed over the carbon grid? Are the
double bonds aromatic or isolated? What is the

0009-2614r98r$19.00 q 1998 Elsevier Science B.V. All rights reserved.

PII: S 0 0 0 9 - 2 6 1 4 Ž 9 8 . 0 0 1 4 4 - 4
54 H. He et al.r Chemical Physics Letters 287 (1998) 53–56
reason for the oxidizing nature of GO? In order to
answer these questions, we have studied the products
of the reaction of GO with potassium iodide in a
neutral medium and of its thermal decomposition at
moderate temperatures, by solid-state NMR.
G O w as prepared by oxidation w ith
KMnO4rH 2 SO4 w16x. The sample was washed with
5% aqueous HCl, dialysed w17,18x for 7 days in the
dark Žwith several changes of the dialysing water.
until the solution was free of sulphate and chloride
ions, dried at 408C in 10y2 Torr vacuum to remove
adsorbed water and finally pulverized and dried in
10y5 Torr vacuum for 2 days at room temperature.
The interlayer distance of the product Ždetermined by
Debye–Scherrer photographs with Ni-filtered Cu K a
Fig. 1. 13 C MAS NMR Bloch decay spectra with high-power
Ž )60 kHz. 1 H decoupling of Ža. GO; Žb. GO–KI; Žc. GO
heat-treated at 1008C in vacuum. The spectra were recorded using
a Chemagnetics CMX-400 spectrometer operating at 100.6 MHz
and an MAS probehead with zirconia rotors 4 mm in diameter
spinning at 5 kHz in nitrogen gas. 458 radiofrequency pulses of 1
ms duration and 20 s recycle delays were used. 13 C chemical
shifts are given in ppm from external tetramethylsilane ŽTMS..
Fig. 2. Reaction of GO with KI.
radiation. was 7.1 A,˚ corresponding to a water con-
tent of 8–15%.
The intensity of the resonances at 60 and 70 ppm
in the 13 C NMR magic-angle-spinning ŽMAS. spec-
trum of GO treated with KI at room temperature for
7 days, washed with water and dried in vacuum for
24 h ŽFig. 1b. is lower than in the parent sample
ŽFig. 1a.. We note that GO reacts with hydroiodic
acid with the liberation of iodine, a reaction used as
a test for the presence of epoxide groups w3,7x.
Deoxygenation of epoxide groups is expected to
reduce the intensity of the peak at 60 ppm. A broad
13
C line centred at 130 ppm Žwith a shoulder to
higher chemical shifts. indicates major structural re-
arrangement, and there is a new peak at 110 ppm.
We suggest that the shoulder above 130 ppm and the
peak at 110 ppm are due to the formation of phenol
andror aromatic diol species w19,20x. Such reactions,
of which iodides are capable w21x, require that: Ž1.
OH functional groupŽs. attached to the carbon ring
are converted to phenolsraromatic diols; Ž2. at least
one double bond is present in the ring or is formed
by deoxygenation of the epoxide; Ž3. bonds are
broken at the position of the OH group during
‘‘rearomatization’’ ŽFig. 2..
A sample of GO was thermally decomposed by
heating in vacuum at 1008C for 24 h. The peaks at
60 and 70 ppm in the 13 C NMR spectrum have
disappeared, and the dominant peak is at 122 ppm,
corresponding to the line at 130 ppm in the parent
sample ŽFig. 1c.. The 110–160 ppm spectral region
resembles that of GO treated with KI ŽFig. 1b.. The
resonances at 110–120 and 160 ppm come from
phenolic groups, indicating deoxygenation. The de-
composition of GO is much more quantitative than
the reaction with KI, but is not accompanied by
 H. He et al.r Chemical Physics Letters 287 (1998) 53–56 55

CO and CO 2 w3x. We believe that, working under

Fig. 3. Model compound for the assignment of the 13 C NMR
spectra of GO. Carbons 1 and 2, carbon 3 and carbons 4 and 5
correspond to C–O–C, C–OH and double bonds in the structure
of GO, respectively.
evolution of oxygen: the products are CO and CO 2 ,
which has been explained in terms of the highly
reactive oxygen atom being released from the GO
structure and reacting with the surface of GO to form
moderate conditions, we have obtained an intermedi-
ate decomposition product of GO. The final product
at higher temperatures is highly disordered oxygen-
containing graphitic carbon w3x, not easily detected
by NMR.
In conclusion, NMR confirms the assignment of
the 70 ppm line to C–OH groups w15x. NMR spectra
of GO treated with KI and the course of its thermal
decomposition strongly argue for the presence of
epoxide Ž1,2-ether. groups, responsible for the 60
ppm line Žand for the oxidating nature of GO.,
instead of 1,3-ethers as suggested by Mermoux et al.
w15x. We note that the formation of 1,3-ethers re-
quires a complex sequence of reactions, unlikely to
be realized in KMnO4rH 2 SO4 . The 130 ppm peak
comes from aromatic entities and conjugated double

Fig. 4. New structural model for Ža. as-prepared GO; Žb. GO after thermal treatment at 1008C for 24 h in vacuum. For clarity, the model
indicates only the chemical connectivity and not the spatial orientation of the functional groups. Hydroxyl groups are perpendicular to the
graphitic plane, and the interplanar space contains also water molecules.
56 H. He et al.r Chemical Physics Letters 287 (1998) 53–56
bonds. The easily oxidized isolated double bonds are
likely to be rare. The formation of epoxides from
polycyclic aromatic hydrocarbons w22x, suggests that
not every aromatic entity contains an epoxide group
and a ring containing such a group will have at least
one unoxidized double bond, as shown by the forma-
tion of phenolic structures in the deoxygenation reac-
tions.
The formation of phenol Žor aromatic diol. groups
during deoxygenation indicates that the epoxide and
the C–OH groups are very close to one another.
Apart from the double bonds, the ‘‘oxidized’’ ben-
zene rings contain an epoxide group and at least one
C–OH group, as found in a natural sesquiterpenoid
compound ŽFig. 3. w23x, in which the 13 C chemical
shifts of the relevant carbon atoms are entirely con-
sistent with our assignment. It is not necessary for
the distribution of functional groups in every oxi-
dized aromatic ring to be identical, and both the
oxidized rings and aromatic entities are distributed
randomly. The layers of GO terminate with C–OH
and –COOH groups, consistent with infrared spec-
troscopic results w24x.
GO is built of aromatic ‘‘islands’’ of variable size
which have not been oxidized, and are separated
from each other by aliphatic 6-membered rings con-
taining C–OH and epoxide groups and double bonds
ŽFig. 4.. Note that the model indicates the chemical
connectivity and not the spatial orientation of the
functional groups. Aromatic entities, double bonds
and epoxide groups give rise to a nearly flat carbon
grid, a conclusion supported by the structure of
smaller epoxide molecules w25–27x. Only the car-
bons attached to OH groups are in a slightly dis-
torted tetrahedral configuration, resulting in some
warping of the layers. The functional groups lie
above and below the carbon grid forming a layer of
oxygen atoms of variable concentration. This ar-
rangement of negatively charged oxygen layers could
prevent nucleophilic attack on carbon atoms explain-
ing the relative chemical inactivity of the epoxide
groups in GO w27x.
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