i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 5 7 4 e3 5 7 9

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Experimental investigation of hydrogen storage in single

walled carbon nanotubes functionalized with borane

D. Silambarasan, V.J. Surya, V. Vasu, K. Iyakutti*

School of Physics, Madurai Kamaraj University, Madurai, Tamil Nadu 625 021, India

article info abstract

Article history: Single walled carbon nanotubes (SWCNTs) dispersed in 2-propanol are deposited on the
Received 21 October 2010 alumina substrate using drop cast method. The deposited SWCNTs are characterized using
Received in revised form the techniques SEM, EDS and FTIR. Then the SWCNTs are functionalized with BH3 using
2 December 2010 LiBH4 as the precursor. FTIR, XPS and CHNS techniques are used to confirm the func-
Accepted 5 December 2010 tionalization. The functional groups are identified from FTIR studies. The various elements
Available online 7 January 2011 present in the functionalized SWCNTs are identified from XPS and CHNS studies. The
functionalized samples are hydrogenated and the hydrogen storage capacity of these
Keywords: samples is estimated using CHNS studies.
Carbon nanotubes Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
Functionalization reserved.
Borane
Hydrogen storage capacity

1. Introduction exists in the form of gas at ambient pressure and temperature,

Nanotechnology is the fastest growing area in materials
science and engineering. Since the nanomaterials have
interesting physical properties, they have attracted great
interest in recent years. The high surface/volume ratio of
these materials has significant implications with respect to
energy storage. The shrinking availability of fossil fuels and
global warming leads to the consideration of hydrogen as the
potential alternative for energy services. Hydrogen is one of
the most abundant elements on earth. Moreover, it is the
lightest element and has the highest energy-to-mass ratio.
There is no pollutant emission during energy production.
Nanostructured materials have potential promise in hydrogen
storage because of their unique features such as adsorption on
the surface, inter- and intragrain boundaries, and bulk
absorption [1,2]. Out of the several carbon nanostructures, the
nanotubes discovered by Iijima [3] are now the major break-
through in the technological development. Since hydrogen
the most appropriate way to store hydrogen is in an adsorbed
form on a suitable media. But the problem while using
hydrogen as the fuel is the lack of hydrogen storage media,
hence the development of advanced hydrogen storage media
is needed. Carbon nanotubes are one of the most promising
materials, can adsorb and release a large quantity of hydrogen
easily, reliably, safely and efficiently [4]. Dillon et al. [5]
discovered that SWCNTs have a high reversible hydrogen
storage capacity. Thereafter many studies have been done
widely [6e11]. The hydrogen storage capacity of boron
substituted carbon nanotubes was investigated by Sankaran
et al. [12] and a maximum of 2 wt% hydrogen storage capacity
was observed by them. Hydrogen storage properties of as-
grown, purified SWCNT and nanocrystalline platinum
dispersed SWCNT have been investigated in the pressure
range of 1e100 bar, at 298 and 125 K, the platinum dispersed
SWCNT showed a hydrogen uptake up to 3.03 wt% at 125 K
and at 78 bar [13]. Lipson et al. [14] reported that, the

* Corresponding author. Tel.: þ91452 2458471x390.

E-mail address: iyakutti@yahoo.co.in (K. Iyakutti).
0360-3199/$ e see front matter Copyright ª 2010, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.12.028
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 5 7 4 e3 5 7 9
electrochemical loading of SWCNTs encapsulated by thin Pd
coating resulted in a storage capacity of 8e12 wt% H2. This
hydrogen absorption occured mainly within the interior of the
SWCNT and depended on the SWCNT type. Hydrogen uptake
study of carbon nanotubes (CNTs) impregnated with TiO2
nanorods and nanotubes has been performed at room
temperature and moderate hydrogen pressures by Rather
et al. [15] and these composites stored up to 0.40 wt% of
hydrogen at 298 K and 18 atm, which is nearly five times
higher the hydrogen uptake of pristine CNTs. Recently [16] the
multi-walled carbon nanotubes (MWCNTs) treated by micro-
wave are used for hydrogen storage and the hydrogen storage
capacity of the MWCNTs increased to nearly 0.35 wt% over
0.1 wt% for the pristine sample and increased further to 0.4 wt
%, with improved stability after subsequent heat-treatment.
Lee et al. [17] activated the MWCNTs using CO2 in the
temperature range 500e1100  C and found that the hydrogen
storage capacity has enhanced to 0.78 wt% when the activa-
tion temperature is increased to 900  C [17]. Rashidi et al. [18]
investigated the effect of purity of CNTs on hydrogen storage.
They observed a maximum hydrogen adsorption capacity of
0.8 wt% in the case of CNTs with 95% purity and it may be
raised up to 1 wt% with some purification. In addition, they
compared the hydrogen storage capacity of CNTs with that of
some activated carbon and reported that, there were no
considerable H2-storage in pure carbon nanotubes and acti-
vated carbon at room temperature. On the theoretical side
Yildirim et al. [19] reported that, the transition metal atoms
adsorbed on SWCNT can store hydrogen molecules up to 8 wt
%. After that, Iyakutti et al. [20,21] suggested that, the CNTs
functionalized with metal hydrides, can be used as a hydrogen
Fig. 1 e a. SEM image of purchased SWCNTs. b. SEM image of SWCNTs after sonication.
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storage medium. Among the hydrides tried BH3 [22] is found to
be more suitable than the other metal hydrides. The present
experimental investigation deals with the hydrogenation of
SWCNTs functionalized with borane which is a follow up of
the above theoretical prediction.
2. Theoretical predictions
As mentioned earlier, BH3 is found to be more suitable than
the other metal hydrides. Functionalization with BH3
enhances the binding energy of hydrogen molecules as well
as increases the storage capacity [22]. BH3 can be deposited
on the SWCNTs using LiBH4 as the precursor. Lithium
borohydride LiBH4, yields diborane on heating [23]. Gener-
ally, boranes are the compounds comprising boron and
hydrogen. The parent member BH3 dimerizes to form
diborane, B2H6. Diborane is a colorless gas at room temper-
ature. It has been reported that at room temperature there is
no isolated monoborane, BH3. It is in equilibrium mixture
with B2H6.
B2H6 4 2BH3
But at very low pressure and at a temperature of about
200  C, a small fraction of B2H6 is cleaved into BH3. So there
is a definite possibility of producing borane. In our case we
deal with a hydrogen storage medium which can operate at
or above room temperature. Though borane is unstable at
room temperature, our theoretical calculations reveal that
(CNT þ BH3) complex is stable [22]. Since BH3 remains in
3576 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 5 7 4 e3 5 7 9

Fig. 2 e EDS analysis.

equilibrium mixture with B2H6, we can use B2H6 4 2BH3 to 3.2. Functionalization
functionalize the SWCNTs. Depending upon their interaction
with SWCNTs they will remain as such or split up into BH3 LiBH4 mixed with di ethyl ether in the ratio of 25 mg/ml is
molecules. On higher coverage of BH3 molecules on SWCNTs taken and is drop casted over the surface of SWCNTs. Then
we can observe dimerization of BH3 molecules, which leads the substrates are heated to 275  C (decomposition tempera-
to the formation of B2H6 or it can remain as BH3. Moreover, ture of LiBH4) for 1 h which yields lithium hydride, boranes
diborane is metastable at normal pressures up to 50  C, it
will decompose into 2BH3 molecules. The existence of B2H6
as such or as 2BH3 depends upon temperature and pressure
in which our system (SWCNTs) is maintained.

3. Experimental

3.1. CNT deposition

The purchased SWCNTs with 99% purity are used for

experiments without any further purification. Alumina
substrates of dimension 19 mm  19 mm  0.65 mm
(alumina substrate was taken as it will not react during the
heating process) are cleaned with ethanol, acetone by means
of sonication for 15 min. SWCNTs were taken with 2-prop-
anol in the ratio of 5 mg/ml. This was then kept in an
ultrasonic bath at room temperature for 1 h to allow the
CNTs to be dispersed uniformly. The dispersed solution is
then deposited drop wise using a micro pipette on the
substrates that are maintained in air w60  C. The highly
volatile 2-proponal gets evaporated leaving SWCNTs on the
substrates. After deposition the substrates are heated to
300  C to remove the impurities if any. The morphology of
the dispersed SWCNTs is analyzed using the SEM pictures
and the functional groups are identified through FTIR. The
weight percentage of the carbon present in our sample is
analyzed by energy-dispersive x-ray analysis (EDS). The SEM
pictures, ED spectrum and FTIR spectrum are shown in Figs. Fig. 3 e a. FTIR image of SWCNTs. b. FTIR image of
1a, 1b, 2 and 3a respectively. SWCNTs functionalized with LiBH4.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 5 7 4 e3 5 7 9
and hydrogen. The presence of BH3 in the functionalized
samples is confirmed by the FTIR study and the corresponding
FTIR spectrum is shown in Fig. 3b. We have used X-ray
photoelectron spectroscopy to find the elements present in
our sample. The weight percentage of the hydrogen present in
our functionalized sample is estimated using CHNS elemental
analysis.
3.3. Hydrogenation
The functionalized sample is loaded in the Seivert like
hydrogenation setup and hydrogenated as detailed below. The
sample is maintained at 50  C for 100 min and the hydrogen is
allowed to flow for 20 min at a flow rate of 3 L/min, and then
the sample is left in the chamber to attain the room temper-
ature. After hydrogenation, the hydrogen content present in
our sample is again estimated using CHNS elemental analysis.
The experiments are repeated for different hydrogenation
conditions. The results are given in Table 1.
4. Results and discussion
Fig. 1a and b show the scanning electron microscopy (SEM)
images of purchased SWCNTs and the dispersed SWCNTs
(sonicated for 1 h in 2-propanol) respectively. The average
diameter of SWCNTs is estimated to be 22 nm. Fig. 2 shows the
ED spectrum of CNT after deposition. From the EDS studies, it
is observed that the wt% of carbon present in our sample is
66.29. The remaining 33.71 wt% of oxygen present in the
sample may be due to CNT deposition in open atmosphere.
The functional groups are determined from the bands
appear in the FTIR spectrum. Fig. 3a shows the FTIR spectrum
of SWCNTs coated on alumina substrates. A broad absorption
peak at 3436 cm1 is attributed due to the hydroxyl group. This
might have resulted from water during the purification. The
peak at 1631 cm1 is due to C]C stretching modes of vibra-
tion. The absorption peak at 1240 cm1 is assigned to CeC
stretching vibration [24].
The FTIR spectrum of SWCNTs functionalized with LiBH4 is
shown in Fig. 3b. The higher the BH3 dispersion, the higher is
its reactivity with SWCNT. If the stretching bonds corre-
sponding to BH3/CNT are more then naturally the reactivity of
BH3 and CNT is more. In addition to the above peaks the new
absorption peak at 2355 cm1 occurs due to asymmetric BeH
stretching [25] in borane complex and a peak at 1182 cm1 has
been assigned to the bending mode of BeH bond in the BH3
group [26]. It is to be noted that the peak corresponding to OH
group is not observed in the FTIR spectrum.
Table 1 e Hydrogenation results.
Time of heating Temperature of
(min) the substrate ( C)
40 100
100 100
100 50
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Fig. 4 e XPS spectrum.
X-ray photoelectron spectroscopy is used to find the
elements present in our sample. The full survey spectrum
for our functionalized sample is shown in Fig. 4. The lower
binding energy component is assigned to boron atoms
bonded only to the other boron atoms [27], whereas the
higher energy component represents the oxidized boron
[28]. The C 1s component at 286.3 eV is assigned to CeO or
CeOH bond [29], a small peak at 290.9 eV is due to Li2CO3.
The main O 1s component is assigned to boron oxide [30].
The de-convolved XPS spectra (Fig. 5) show the individual
components. The hydrogen storage capacity of the hydro-
genated samples is estimated using CHNS elemental
analysis in the machine e Elementar Vario EL III e
Germany.
If oxygen were to absorb H2 then OH groups will appear in
the FTIR spectrum. Obviously the peak corresponding to OH
group is not appearing in the FTIR spectra (Fig. 3b). Therefore,
the hydrogen absorption is mainly due to carbon. The portion
of boron absorption attributed to the presence of oxygen is
determined from the XPS of the functionalized sample and the
wt % of boron is 3.7.
The hydrogenation results (Table 1), we have got are
encouraging. There is a lot of scope for improvement since
there are four parameters involved and are to be optimized for
the maximum hydrogen storage capacity. Also from the EDS
studies, it is observed that the wt% of carbon present in our
sample is 66.29. The remaining 33.71 wt% of oxygen present in
the sample may be due to CNT deposition in open atmo-
sphere. This can be avoided by annealing the samples in inert
atmospheric conditions. This will also improve the hydrogen
storage capacity.
Flow rate Flow duration Storage capacity
(liter/min) (Min) (wt%)
1 4 0.68
1 20 0.87
3 20 1.5
3578 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 3 5 7 4 e3 5 7 9

5. Conclusion

The SWCNTs have been successfully functionalized with BH3

as predicted theoretically using LiBH4 as the precursor. From
XPS studies, the presence of Li, B, and O are observed in our
samples. The presence of BH3 is confirmed using FTIR studies.
The hydrogen storage capacity of the functionalized SWCNTs
is found to be 1.5 wt% at 50  C. The hydrogen absorption is
mainly due to carbon. Hydrogenation depends upon various
parameters which are to be optimized to achieve maximum
hydrogen storage capacity. Surely, we will be able to achieve
the 2015 DOE target.

Acknowledgments

Author DS thanks Madurai Kamaraj University (MKU) for

USRF. The authors VV and KI thank MKU and UGC-UPE. The
authors KI and VJS thank Council of Scientific and Industrial
Research (CSIR) for financial assistance under Emeritus
Scientist Scheme. The financial assistance by Asian Office of
Aerospace Research and Development (No. 09-4157) and the
help by Dr. R. Ponnappan, the project manager are acknowl-
edged with thanks.

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