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A rapid and efficient method to prepare exfoliated graphite

by microwave irradiation

Tong Wei, Zhuangjun Fan*, Guilian Luo, Chao Zheng, Dashou Xie
Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, School of Materials Science and Chemical Engineering,
Harbin Engineering University, Harbin, Heilongjiang 150001, China

A R T I C L E I N F O A B S T R A C T

Article history:
Received 26 February 2008
Accepted 9 October 2008
Available online 17 October 2008
Exfoliated graphite materials had been rapidly and efficiently prepared by microwave irra-
diation in a short time (about 4 min including 3 min mixing and 1 min microwave irradia-
tion). The promotion of the intercalation by microwave irradiation was proven by X-ray
diffraction. With increasing content of oxidant and intercalation agent, the expanded vol-
ume of exfoliated graphite increased at first and then decreased. When the weight ratio
of natural graphite and nitric acid to potassium permanganate was set at 1:2:1, the
expanded volume of exfoliated graphite reached the maximum value (312 mL/g) and sorp-
tion capacity of this exfoliated graphite was 56 g of engine oil and 32 g of kerosene per 1 g of
exfoliated graphite.
 2008 Elsevier Ltd. All rights reserved.

Exfoliated graphite (EG) is a promising material, which has
been widely used as gasket, thermal insulator, fire-resistant
composite, etc. [1]. Recently, such material was reported to ex-
hibit excellent adsorption for spilled oil in water [2]. In general,
EG is prepared by rapid heating of graphite intercalation com-
pound (GIC), resulting in the abrupt ejection or decomposition
of guest molecules and the subsequent huge unidirectional
expansion of the initial platelets. The most conventional heat-
ing source is flame through which the GICs are transported.
However, alternative methods including coupled plasma, laser
irradiation and microwave (MW) irradiation are also proposed
[3]. Among them, MW irradiation is very promising, because it
can be performed at room temperature in a short time with
less consuming energy. Several groups [4–6] have used MW
irradiation to produce EG. However, all of their studies need
either a lot of time (more than 4 h) to prepare GICs [4,5] or
time-consuming and contaminative water rinsing and desic-
cation before MW irradiation [6]. In this work, we reported a
rapid and efficient route to prepare EG by MW irradiation. Un-
like previous reported methods, the natural graphite (NG), oxi-
dant and intercalation agent were only simply mixed before
MW irradiation, and the intercalation and exfoliation were
all accomplished in 60 s under MW irradiation. The resulted
EG had a large expansion volume and oil adsorbing capacity.
The effects of oxidant and intercalation agent on the ex-
panded volume of EG were also investigated.
NG (purity of 99%, average flake size of 320 lm, produced
in Man Country, China), nitric acid (68%) and potassium per-
manganate were mixed by a glass bar at different weight ra-
tios in a porcelain dish at room temperature for 3 min. After
that the porcelain dish was directly placed into a domestic
MW oven (Haier China) and irradiated at 700 W for 60 s. For
comparison, the above mixed precursor was also put into a
tubular furnace at 1000 C for 1 min. Besides, H2O2 and
H2SO4 were also used as oxidant and intercalate for prepara-
tion of EG by MW irradiation. The exfoliation volume was
determined by measuring the volume of the EG prepared from
0.2000 g NG.

* Corresponding author: Fax: +86 451 82569890.

E-mail address: fanzhj666@163.com (Z. Fan).
0008-6223/$ - see front matter  2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2008.10.013
338 CARBON 4 7 ( 2 0 0 8 ) 3 1 3 –3 4 7

intercalating agent is other important factor that affects the

Fig. 1 – SEM image of EG (no. 2) prepared by MW irradiation.
Under MW irradiation, a marked exfoliation of the precur-
sors is accompanied by fuming and lightening. The worm-like
structure of sample is clearly observed by SEM (JEOL JSM-
7401F), as shown in Fig. 1. The surface morphology of sample
exhibits well exfoliated structure to prove full and regular
expansion in direction of c-axis.
Table 1 shows the expanded volume and bulk density of EG
prepared under MW irradiation. The maximum expanded vol-
ume (312 mL/g) is obtained for no. 8. The bulk density of this
sample is 5.4 · 103 g/cm3, which is close to that of EG
intercalation process and finally has influence on the ex-
panded volume of EG. Potassium permanganate is strong oxi-
dant, and the oxidation ability has relation with its
concentration and solution acidity. Therefore, with the in-
crease of the amount of potassium permanganate used in
the reaction, the expanded volume of the EGs increases rap-
idly (from nos. 1 to 5 in Table 1). When the amount of potas-
sium permanganate is excessive, strong oxidation would
damage the structure of the graphite layers [8], and the ex-
panded volume would be decreased (see no. 6 in Table 1). In
this system, HNO3 not only functions as intercalate but also
provides acidity to promote the oxidation ability of KMnO4.
When the amount of HNO3 increases, much more HNO3 is
intercalated into the gallery of graphite and expanded volume
of EG increases. However, superfluous HNO3 may result in
excessive oxidation of graphite layers and the consequent de-
crease of expanded volume (see no. 9 in Table 1). For compar-
ison, the precursor after simple mixing for 3 min was also
exfoliated by rapid heating to 1000 C. As can be seen from
no. 10 in Table 1, the precursor can also be exfoliated, and ex-
panded volume is only 160 mL/g. If this precursor was exfoli-
ated by MW irradiation, expanded volume is 275 mL/g. This is
the evidence for the promotion of the intercalation by MW
irradiation.
In order to further confirm this supposition, the samples
were also investigated by X-ray diffraction (XRD, CuKa radia-
tion) as shown in Fig. 2. In this work, KMnO4 is used as oxi-
dant and HNO3 as intercalation agent, hence the resulted


GIC is graphite nitrate Cþ 
24n  NO3  mHNO3 [9]. The reflections

(5.1 · 103 g/cm3) prepared under MW irradiation [4] and low-
er than that of EG (6 · 103–10 · 103 g/cm3) prepared com-
mercially by rapid heating accompanied by reaction in
oxidizing agent-sulfuric admixture [7]. The intercalation and
exfoliation of the precursors are accomplished in 60 s under
MW irradiation. Since the edge of graphite must be oxidized
and opened before intercalation, strong oxidant, which has
high oxidation rate, must be used for successful intercalation
in a short time. When H2O2 instead of KMnO4 is used as oxi-
dant, there is no expansion of the precursor due to its low oxi-
dation ability (see no. 11). The amount of oxidizing agent and
of both graphite and GIC indicate the partial intercalation of
graphite by HNO3 after simple mixing for 3 min as shown in
Fig. 2b. The XRD data on GIC are well explained by stage the-
ory. The basal spacing (Ic) calculated by Bragg equation and
I c ¼ ½d i þ 3:35ðn  1Þ=l (di is the interlayer distance, n is the
stage number) is 1.325 nm. In the case n = 3, the interlayer dis-
tance calculated is 0.655 nm, which is equal to that of


Cþ 
24n  NO3  2HNO3 [9]. Whereas, after 20 s MW irradiation
(see Fig. 2c), the (0 0 2) reflection of graphite disappears, and
the (0 0 4) reflection of stage 3 GIC shifts left. The basal spacing
and interlayer distance of GIC increased to 1.418 and 0.748 nm

Table 1 – Expanded volume and bulk density of EG prepared under MW irradiation

No. Mixture ratioa (by weight) A:B:C Exfoliation method Expanded volumec (mL/g) Bulk densityc (*103 g/cm3)

1 1:1.5:0.1 MW 158 9.8

2 1:1.5:0.2 MW 202 7.5
3 1:1.5:0.4 MW 232 7.0
4 1:1.5:0.8 MW 247 6.5
5 1:1.5:1 MW 293 5.7
6 1:1.5:1.5 MW 268 6.1
7 1:1:1 MW 236 6.8
8 1:2:1 MW 312 5.4
9 1:2.5:1 MW 275 5.9
10 1:2.5:1 Rapid heating to 1000 C 160 11.4
b
11 NG:H2SO4:H2O2 = 1:2:1 MW No expansion –
a A, NG; B, nitric acid; C, potassium permanganate.
b Mixture ratio (by weight).
c Three specimens of each type were tested, and the average value was obtained (the relative deviation is less than 5%).
 CARBON 4 7 (2 0 0 8) 3 1 3–34 7 339

with that of Kown’s work (55 g of diesel oil (200–400 mPa s)

Relative Intensity(a.u.)
d

III(004)

G(002)
per 1 g of EG with bulk density of 5.1 · 103 g/cm3) [4].

III(004)

G(002)
c
In conclusion, EG materials had been rapidly and effi-
b ciently prepared by MW irradiation in a short time (about
Relative intensity (a.u.)

4 min including 3 min mixing and 1 min MW irradiation) with

a
less consuming energy. The maximum expanded volume of
20 25 30 35
EG is up to 312 mL/g and sorption capacity is found to be
III(005)
2θ ( degrees)
III(001)

III(002)

III(009)
56 g of engine oil and 32 g of kerosene per 1 g of EG. Therefore,

G(004)
d such material may be promising in commercial application
for oil sorption because of its low cost and simple fabrication.
c

b
Acknowledgements
a
10 20 30 40 50 60 70 Supports from Key Project of Chinese Ministry of Education
2θ (degrees) (No. 106011), Foundation of Harbin Innovation Fellow
(2006RFQXG030 and 2007RFQXG028) and Fundamental Re-
Fig. 2 – XRD patterns of samples (no. 5): (a) NG; (b) mixture
search Foundation of Harbin Engineering University (Project
before MW irradiation, and after (c) 20 s and (d) 60 s of MW
HEUFT07094) are appreciated.
irradiation (G means graphite and I means stage 3 GIC).

R E F E R E N C E S
(the interlayer distance of Cþ 
24n  NO3  5HNO3 is 0.780 nm [9]).
This is the evidence of successful intercalation promoted by
MW irradiation, which results in the improvement of ex-
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