Advances in Chemical Engineering and Science, 2013, 3, 4-6
http://dx.doi.org/10.4236/aces.2013.33A3002 Published Online August 2013 (http://www.scirp.org/journal/aces)
Room Temperature Storage of Methane by Bamboo-Like
Carbon Nanotubes
Mitsunori Furuya, Kenji Ichimura
Graduate School of Science and Technology, Kumamoto University, Kumamoto, Japan
Received May 9, 2013; revised June 9, 2013; accepted July 9, 2013
Copyright © 2013 Mitsunori Furuya, Kenji Ichimura. This is an open access article distributed under the Creative Commons Attribu-
tion License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited.
ABSTRACT
Single carbon nanotubes (CNTs) have the sorption states at around 200 K, and show the poor desorption characteristics
at around 300 K. The bamboo-like CNTs, HP1050 and the ground HP1050 (HP-1050G), show the desorption peaks at
around 100 K and 140 K, respectively. Furthermore, HP1050G has the sorption states at around 300 - 400 K. On the
basis of the sorption process, the ground bamboo-like CNT has a possibility for application to the room temperature
storage of methane, which has utility for energy technologies such as fuel cells.
Keywords: Methane; Storage; Carbon Nanotube; Absorption States
1. Introduction
Methan storage characteristics in porous metal-organic
frameworks have been reported [1].
We have reported the chemical interactions or storage
of hydrogen and of rare gases, such as He, Ne, and Ar, in
solid carbon nanotubes [2]. Closed carbon nanotubes
(CNTs) show larger amounts of absorption for gases
such as hydrogen, He, Ne, and Ar than opened CNTs.
From these results, we conclude that sites preferentially
found in endcaps are more active for the chemical inter-
action between rare gases and solid carbon nanotubes.
Recently, bamboo-like CNTs that have many endcap
structures have been produced in large quantity [3]. Ac-
cording to the above-mentioned results, these kinds of
CNTs are expected to have strong interactions for gases.
On the basis of the sorption characteristics for CNTs,
we examined the thermal desorption of methane from
CNTs or the sorption abilities of CNTs for methane.
2. Experimental
Capped and open (no endcaps) single wall carbon nano-
tubes (CSWCNT and OSWCNT, Bucky USA BU-202
(endcaps) and BU-203 (no endcaps), respectively, with
1.4 - 3 nm diameter and 10 - 50 μm length) were used
without further purification for the adsorption studies.
The only difference between BU-202 and BU-203 is the
endcap structure at both ends, and otherwise the two
structures are the same.
The synthesis of CNT with a high density of bamboo
structures, HP1050, was carried out in a quartz-tube re-
actor [3]. Figure 1 shows the TEM image of sample
HP1050. For each synthesis run, 100 mg of the catalyst
powder was spread on to a Mo boat (40 × 100 mm2).
Prior to rising the temperature, the reactor chamber was
flushed with N2 flowing at 100 sccm for 20 minutes.
Then the growth of nanotubes was performed by flowing
gas mixtures of N2 (100 sccm), NH3 (40 sccm) and C2H2
(10 sccm) at 1050˚C and 760 Torr for 2 h. Sample
HP1050G was obtained from HP1050 using a ball mill at
room temperature under ambient conditions. The TEM
image of HP1050G was almost the same as Figure 1.
The specific surface area was measured by means of the
N2 BET method at 77 K.
After vacuum heating at 653 K or 1073 K, the samples
were exposed to methane (Nippon Sanso, >99.9% purity)
of 1 to 1.4 atm, at 473 K for 3 - 5 days. After the sample
was cooled to liquid nitrogen temperature, the sample
tube was evacuated to ultra-high vacuum. Desorbed
gases were analyzed by using two mass-spectrometers
when the sample was heated at a temperature-rise rate of
5 K/min.
3. Results and Discussion
Figure 2 shows the thermal desorption of methane from
CNTs. Methane desorption is confirmed from the frag-
mentation in the mass number regions 1 - 2 and 12 - 16.
C
opyright © 2013 SciRes. ACES

M. FURUYA, K. ICHIMURA 5
Figure 1. TEM image of HP1050.
No significant signals of hydrogen and hydrocarbon are
detected. In order to avoid an influence of O+ from H2O,
methane desorption is recorded by monitoring the mass
number of 15.
Among the various CNTs, SWCNTs show relatively
strong interactions for hydrogen [2]. From Figure 2, the
desorption of methane by a van der Waals interaction is
observed at around 100 K. Additional desorption peaks
appear at around 180 K and 220 K for the closed and
open SWCNTs, respectively. Since the desorption occurs
at higher temperatures than the boiling point of methane,
111.7 K, this desorption is considered to be due to an
extended van der Waals interaction between ad-/ab-sor-
bed methane and CNT. A broad desorption, due to che-
mical interaction/bonding, was also observed at around
900 K and 1000 K, respectively, for the closed and open
SWCNTs. The ad-/ab-sorption characteristics at around
180 - 220 K and 900 - 1000 K for SWCNTs are, respec-
tively, useful for low temperature storage and gettering
(vacuum-pumping) applications.
The bamboo-like CNT, HP1050 showed a clean ther-
mal desorption peak for methane at 95 K, due to the van
der Waals interaction. Although thermal desorption is a
kinetic measurement method and the ad-/ab-sorption am-
ount at equilibrium cannot be determined, thermal desor-
ption gives important information about the ad-/ab-sor-
ption states, and at least the amount of ad-/ab-sorption
remaining under ultra-high vacuum conditions can be
evaluated. As shown in the inset to Figure 2, the bam-
boo-like CNTs show desorption of methane in the tem-
perature range 220 - 650 K, and HP1050G shows a
stronger effect than HP1050. A stronger extended van
der Waals interaction is realized in bamboo-like CNTs.
The high temperature desorption observed for the
SWCNTs almost disappears for the bamboo-like CNTs.
On the other hand, the ground bamboo-like CNTs,
HP1050G, show a thermal desorption peak at 144 K.
0100 200 300 400 500 600 700 800 900100011001200
0.0
5.0x10-7
1.0x10-6
1.5x10-6
2.0x10-6
2.5x10-6
HP1050
HP1050G
Pressure / mbar
Temperature / K
0.0
2.0x10-8
4.0x10-8
6.0x10-8
8.0x10-8
1.0x10-7
1.2x10-7
1.4x10-7
1.6x10-7
1.8x10-7
CSWCNT
OSWCNT
Pressure / mbar
Figure 2. Thermal desorption of methane from SWCNTs
and bamboo-like CNTs. The inset show the desorption in
the temperature range 220 - 650 K.
Since the peak temperature is higher than the boiling
point of methane, the mechanism for this desorption
should be assigned to the extended van der Waals inter-
action. The grinding treatment causes a shortening of the
tube as observed in TEM images and causes the specific
surface area to increase from 21 m2/g to 245 m2/g. The
grinding treatment changes the properties of the bam-
boo-like CNT, and presumably exposes more bamboo
cap surfaces to the methane gas. Active sites having new
electronic states and nano-space are considered to be
generated in the bamboo joints, wall-cap joints, as seen
in Figure 1.
Furthermore, as shown in the inset figure, new absorp-
tion states were observed at around 350 K for HP1050G.
The reason for this methane absorption is considered to
be due to a super van der Waals interaction or weak
chemical bonding between the ad-/ab-sorbed methane
and the CNT. The high temperature desorption observed
for the SWCNTs also disappears for the bamboo type
tubes.
In thermal desorption method, the amount of desorp-
tion was calculated by using the pumping rate, the meas-

M. FURUYA, K. ICHIMURA 6
Table 1. Amounts of desorption of Methane (mol) per gram
CNTs in nominal three temperature regions: low, medium,
and high temperatures.
Sample T < 250 K 250 K, T < 450 K 450 K < T
CSWCNT 0.2 0.03 1.8
OSWCNT 0.2 0.06 3.1
HP1050 6.6 0.02 0
HP1050G 11.3 1.1 0
Units: ×10−5 mol CH4/g CNTs.
urement volume and the sensitivity. The amount of de-
sorption means a remained amount under the high-va-
cuum measurement conditions. However, this suggests
the comparison for the sorption characteristics among
CNTs. The amounts of desorbed methane are evaluated
by using the values of the integrated desorption area,
background pressure, pumping speed, system volume,
and sensitivity, and the results are listed in Table 1.
Since the amount of desorbed methane means the amount
remaining after of ad-/absorption under high-vacuum
conditions, the ad-/ab-sorption amount at equilibrium is
expected to increase at high methane pressures at around
room temperature. At least, room temperature storage
requires ad-/ab-sorption states at around room tempera-
ture. HP1050G satisfies this requirement. HP1050G
shows a larger amount of desorption than HP1050, the
active sites are assigned not to the tube or bundle struc-
ture but rather to the endcap-like structure of the joint or
gnarl of the bamboo feature. Noble electronic states ap-
pear in the endcap-like structure of the joint or gnarl of
the bamboo feature in HP1050G.
4. Conclusions
The bamboo-like CNTs, HP1050 and the ground HP1050
(HP-1050G), show the desorption peaks at around 100 K
and 140 K, respectively. Furthermore, HP1050G has the
sorption states at around 300 - 400 K. By using the spe-
cial characteristics of the sorption for the ground bam-
boo-like CNT, the room temperature storage of methane
can be realized.
5. Acknowledgements
Authors thank Dr. W. Z. Li and Associate Professor Z. F.
Ren of Department of Physics, Boston College for the
sample supply of the bamboo-like CNTs.
REFERENCES
[1] W. Zhou, “Methane Storage in Porous Metal-Organic
Frameworks: Current Records and Future Perspectives,”
The Chemical Record, Vol. 10, No. 3, 2010, pp. 200-204.
doi:10.1002/tcr.201000004
[2] K. Ichimura, K. Imaeda, C.-W. Jin and H. Inokuchi, “Su-
per van der Waals Interaction of Fullerenes and Carbon
Nanotubes with Rare Gases and Hydrogen-Storage Char-
acteristics,” Physica B: Condensed Matter, Vol. 323, No.
1-4, 2002, pp.137- 139.
doi:10.1016/S0921-4526(02)00879-7
[3] W. Z. Li, J. G. Wen and Z. F. Ren, “Effect of Tempera-
ture on Growth and Structure of Carbon Nanotubes by
Chemical Vapor Deposition,” Applied Physics A, Vol. 74,
No. 74, 2002, pp. 397-402.
doi:10.1007/s003390201284