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X-Ray Difraction Pattern of Graphite Oxide

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2013 Chinese Phys. Lett. 30 096101
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CHIN. PHYS. LETT. Vol. 30, No. 9 (2013) 096101

X-Ray Diffraction Pattern of Graphite Oxide

MU Shi-Jia(), SU Yu-Chang()** , XIAO Li-Hua(), LIU Si-Dong(),

HU Te(), TANG Hong-Bo()
School of Materials Science and Engineering, Central South University, Changsha 410083

(Received 6 May 2013)

X-ray diffraction patterns of graphite oxide (GO) are theoretically simulated as a function of the displacements
of carbon atoms using the DebyeWaller factor in terms of the WarrenBodenstein equation. The results demonstrate that GO has the turbostratically stacked structure. The high order (00l) peaks gradually disappear with
the increase in atomic thermal vibrations along -axis while the (0) ones weaken for the vibrations along a-axis.
When the displacement deviation = 0.015 nm and = 0.100 nm the computed result is consistent with the
experimental measurements.

PACS: 61.05.cp, 61.46.Df, 07.05.Tp

DOI: 10.1088/0256-307X/30/9/096101

Graphite oxide (GO), which is a layered material,

produced by chemical oxidation of graphite (G) in the
presence of strong acids and oxidants,[13] has been
widely used in preparation of single or few layers of
graphenes and their composite materials.[47] GO consists of graphene oxide sheets with some oxygenated
functional groups.[8] It is now generally accepted that
hydroxyl and epoxy groups are on the basal planes
while carbonyl and carboxyl groups are at the edges.[9]
A turbostratically stacked system consists of the
individual sheets, which are parallel to each other by
the same interlayer distances, but random in translation parallel to the layer and in rotation about the
normal to the sheets. The typical X-ray diffraction
(XRD) patterns of the materials just contain the (00)
and (0) peaks and without any three-dimensional
() peaks.[1013] This phenomenon can be well explained by the WarrenBodenstein (WB) equation,[14]
coh () =

1 2 sin(2 )
()

2

) (),
+2
2 ()(1

0.2427
() =

(1)

(arccos 1 2 ) sin(2),

+ ()2 , =

2 ()2 / ,

where = 2sin/, coh () is the coherent scattering

intensity, () the atomic scattering factor, the
number of atoms in a sheet, the number of identical layers, the interatomic distance between two
atoms and , the interlayer distance and the
size of atomic plane.
It has been characterized by scanning electron microscopy (SEM) and transmission electron microscopy

(TEM) that GO has well-packed layers.[15,16] XRD

characteristics further demonstrate that its structure
is a turbostratically stacked system (from Fig. 1).
However, the feature cannot be completely explained
by the WB equation, because some high order (00)
diffraction peaks, such as (003), (004), (005), do not
disappear via the equation (first curve in Fig. 2), which
does not meet the experimental results, as shown in
Fig. 1. We find that if the atomic thermal vibrations
are considered, this problem can be solved very well.
Thus, in this Letter we study the XRD pattern of GO
on the basis of the WB equation.
In terms of the simulation of the WB equation,
in order to simplify the model, GO is regarded as an
expandedly turbostratic stacking nanographite. The
oxygenated functional groups just expand the interlayer distances. A similar model has been successfully applied to the investigation of intercalation compounds XRD patterns.[10]
In Eq. (1), the first term represents the intralayer
interference, defined as intra (), which consists of
(0) diffraction lines. The second one represents the
interlayer interference effect, defined as inter () and
made up of (00) peaks. When the DebyeWaller
factor is taken into account, the thermal vibration
of carbon atoms will reduce the coh ().[12] GO is
anisotropic and coh () only influenced by intra () and
inter (). Thus, for intra (), the DebyeWaller factor
is expressed as
1 = exp[16( sin /)2 ],
and for inter (), it is expressed as
2 = exp[16( sin /)2 ],
where and are the displacements of carbon
atoms along the and axes. Total coh () reads

* Supported

coh () = 1 intra () + 2 inter ().

(2)

by the Innovation Foundation of the Ministry of Science and Technology of China under Grant No 10C26224302621.
author. Email: ychsu@mail.csu.edu.cn
2013 Chinese Physical Society and IOP Publishing Ltd
** Corresponding

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CHIN. PHYS. LETT. Vol. 30, No. 9 (2013) 096101

On the other hand, the incoherent scattering intensity

inc () also needs to be considered[11,12] and it is approximated by the Hajdus equation[17] multiplied by
the Ruland attenuation function.[18] If the background
scattering is ignored, total scattering intensity can be
expressed as
(3)

where is the scale coefficient and () is the product of absorption factor and polarization factor. The
theoretical scattering intensity can be computed by
combination of Eqs. (1)(3).

20

40
2

50

(100)
0.0350 nm

40

45

50

55

60

65

60

70

80

(deg)

1389

(001) (002)
(001) (002)

(003)
(003)

(005)

2927
-CH2-

3500

3000

2500

2000

10 15 20 25 30 35
(deg)

Experiment
Simulation

(110)
(110)

50

60
2

70

80

(deg)

Fig. 2. Simulated XRD patterns of the GO with different values of . Fixed parameters = 0.154 nm, 0 =
0.246 nm, = 0.855 nm, = 5.169 nm, = 0.0055 nm
and = 17.

GO was prepared by the Hummers method.[3] Figure 1 shows the experimental XRD patterns of the
G and GO, which are obtained by an XRD diffractometer (D/Max-2500) with Cu radiation ( =
0.154 nm). The interlayer distance obtained from the
(002) peak is 0.335 nm (2 = 26.60 ) in G. This is
markedly expanded to 0.855 nm (2 = 10.34 ) after
oxidation to form GO. Three-dimensional () peaks
such as (101), (102), (103) and (112) are obvious in
G, but absent in GO with only (00) and (0) ones
left. This means that GO is a turbostratically stacked
material and its structure should be explained by the
WB equation.

1000

Fig. 4. FTIR spectra of the GO.

(110)

(100)

40

1500

-1

(110&(007))

(100)

1054
O
-C -C -

(-OH)

(006)

(100)

(001)

(100&(004))

1223
C -O

3420

Intensity (arb. units)

(002)

85

(-OH)

4000

= 0.011 nm
0.066 nm
0.100 nm
0.150 nm

(b)

25 (arb. units)

Intensity (arb. units)

(001)

80

2363 2339
1644
=C-H
1717 C=C
2854
C=O

Wavenumber (cm
= 0.011 nm
0.066 nm
0.100 nm
0.150 nm

75

(112)

Fig. 1. Experimental XRD patterns of the G and GO.

(a)

70

(deg)

(006)

(103)

(100)

30

(110)

0.0250 nm

(001)

10

(100)

35

GO

(002)

(110)

0.0150 nm

Transmittance (arb. units)

Intensity (arb. units)

(004)

(100) (101)
(102)

(110)

0.0055 nm

(100)

Fig. 3. Simulated XRD patterns of the GO with different values of . Fixed parameters = 0.154 nm, 0 =
0.246 nm, = 0.855 nm, = 5.169 nm, = 0.100 nm
and = 17.

G
(002)

Intensity (arb. units)

= [coh () + inc ()] (),

(100)

(100)
(001)
(110)

(002)

10

20

40

30

50

40
2

60

50

70

60

80

70

80

(deg)

Fig. 5. Comparison between the simulated XRD pattern

of GO and the experimental one with an inset that enlarges the 2 range of 3585 .

Figure 2 shows the simulated XRD patterns of GO

with different values of . These fixed parameters are
the experimental data from Fig. 1 except . In general, = 0.0055 nm and = 0.011 nm[12] should
have been used to compute the intensity of GO. In
fact, those high order (00) peaks, where >2, do not
vanish, which do not meet the experimental results in
Fig. 1. These peaks gradually fade away with the increase of , e.g., when =0.100 nm, only (001) and

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CHIN. PHYS. LETT. Vol. 30, No. 9 (2013) 096101

(002) peaks are left. This demonstrates that after oxidation the scattering characteristic of (00) peaks is
mainly decided by atomic thermal vibration along the
-axis.
The effect of atomic thermal vibration along the axis is shown in Fig. 3. As the (0) diffractions just
occur in the high angle section, 2 is selected from
35 to 85 . In addition, in order to avoid the effect
of (00) diffractions, = 0.100 nm is chosen among
the fixed parameters, obtained from Fig. 2. With the
increase of , the intensity of (110) peak is reduced,
when = 0.0250 nm, the peak is dim. Moreover, its
variation is more obvious than the (100) peak, meeting the experimental results (GO in Fig. 1). However,
considering that the thermal vibration along the axis is small as the strong atomic interactions are in
the basal planes, the effect of on (0) peaks is
limited.
We think that the scattering characteristic of GO
can be attributed to two mechanisms. One is that
after oxidation, carbon atom interactions decrease.
According to the work described by Erickson,[19]
when GO is exfoliated to form graphene oxide,
the high-resolution transmission electron microscopy
(HRTEM) images have demonstrated that the connection forces among carbon atoms are reduced and
some atoms even removed from the basal plane to
form the holes. Thus carbon atoms easily deviate
from the normal positions as a result of thermal vibration. Another reason is attributed to the introduction
of oxygen-containing functional groups to GO. Figure 4 shows the FTIR spectra of GO, exhibiting all
the groups, characterized by the FTIR spectrometer
(Nicolet-6700). With the introduction of oxygenated
groups, such as C = O and CO, on the one hand
the interlayer distance is expanded, which favors the
atomic vibration along the -axis, and on the other
hand the carbon atoms vibrate more easily with the
thermal vibration of oxygenated groups. Furthermore,
as most groups are on the basal planes and a few at
the edges,[9] the vibrations along the -axis are more
violent than those along the -axis. Thus the (00)
scatterings are much more easily affected by the thermal vibrations than the (0) ones.

When the parameters = 0.015 nm and =

0.100 nm (others described by the above work), the
simulated XRD pattern of GO agrees with the experimental one, as shown in Fig. 5. The differences
may be attributed to the constitution of experimental GO that is made up of diverse graphite oxides
(GOs) with different grain sizes and crystallographic
parameters,[11,20] which will be studied further.
In summary, the XRD pattern of GO has been
simulated by the WB equation. The results demonstrate that GO has the turbostratically stacked structure and its scattering intensity is strongly affected by
the thermal vibration of carbon atoms. The high order (00) peaks gradually disappear with the increase
of vibrations along the -axis while the (0) ones
weaken as the vibrations are along the -axis. When
the deviated values = 0.015 nm and = 0.100 nm
the computed result accords with the experimental
measurements.

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