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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0

Available online at www.sciencedirect.com

journal homepage: www.elsevier.com/locate/he

Investigation of single-walled carbon nanotubes-

titanium metal composite as a possible hydrogen
storage medium

D. Silambarasan a, V.J. Surya b, V. Vasu a,*, K. Iyakutti c

a
School of Physics, Madurai Kamaraj University, Madurai 625021, Tamil Nadu, India
b
New Industry Creation Hatchery Center, Tohoku University, Sendai 980-8579, Japan
c
Department of Physics & Nanotechnology, SRM University, Kattankulathur 603203, Tamil Nadu, India

article info abstract

Article history: The present experimental work deals with the investigation of hydrogen uptake study of
Received 28 June 2013 single-walled carbon nanotubes (SWCNTs-Ti)-titanium metal composite. The mixture
Received in revised form containing SWCNTs and Ti powder is made into tablet by cold pressing. The composite has
28 August 2013 been prepared and hydrogenated by evaporating the tablet in hydrogen ambient on glass
Accepted 3 September 2013 substrates using electron beam (EB) evaporation technique. Efficient hydrogen uptake of
Available online 3 October 2013 4.74 wt.% is achieved with the composite and the adsorbed hydrogen posses the average
hydrogen binding energy of 0.4 eV. The obtained hydrogen uptake is due to the cumulative
Keywords: adsorption of hydrogen by CNTs and Ti nanostructured materials. The physical properties
SWCNTs-Ti Composite are characterized by transmission electron microscopy (TEM), atomic force microscopy
Hydrogen storage (AFM), X-ray diffraction study (XRD), scanning electron microscopy (SEM), energy disper-
Electron beam evaporation sive X-ray spectroscopy (EDS) and Raman analysis. Hydrogenation and dehydrogenation
Desorption temperature behavior of the composite are studied using CHN-elemental analysis and thermo gravi-
Binding energy metric/thermal desorption spectroscopy (TG/TDS) studies, respectively. The stored
hydrogen is found to be 100% reversible in the temperature range of 160e310
C.
Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction
Hydrogen is a potential emission-free alternative fuel, which
can reduce dependence on fossil fuels and significantly reduce
the green house gases [1,2]. The cautious storage and delivery
of hydrogen are the problems associated with the relatively
advanced storage methods such as high-pressure gas or liquid
etc. The storage of hydrogen on nanostructures has potential
advantages over those methods. The properties such as high
surface area, molecular sized pores, light weight, chemical
and mechanical stability offered by carbon nanotubes (CNTs)
make them as one of the better aspirants for the storage of
hydrogen [3e5]. Initially in 1997, Dillon et al. [6] have reported
the study of hydrogen storage on CNTs. Following that
remarkable work, intensive research has been carried out on
CNTs to store hydrogen [7e10]. Rzepka et al. [7] have investi-
gated the hydrogen storage capability of micro porous carbon
materials and they obtained a maximum gravimetric storage
capacity of 1.3 wt.% at a pressure of 10 MPa. Hydrogen
adsorption on crystalline ropes of single-walled carbon
nanotubes (SWCNTs) has been examined by Ye et al. [8] and
more than 8 wt.% of hydrogen was stored at pressures higher
than 40 bar at 80 K. Simulation study based on density func-
tional theory (DFT) investigated by Arellano et al. [9] have

* Corresponding author. Tel.: þ91 94437 96898.

E-mail address: vvasumku@gmail.com (V. Vasu).
0360-3199/$ e see front matter Copyright ª 2013, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijhydene.2013.09.009
 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0
reported the interaction of molecular and atomic hydrogen
with (5, 5) and (6, 6) SWCNTs. The physisorbed hydrogen
molecule has the binding energies in the range of 0.04e0.07 eV.
Cabria et al. [10] have studied the adsorption of molecular
hydrogen on the outer surface of (5, 5), (6, 4), (8, 1) and (16, 2)
CNTs using DFT calculations and achieved the hydrogen
adsorption of 14.3 wt.% with the hydrogen binding energies
between 40 and 80 meV. Even a higher storage capacity had
been achieved in most of those studies, the nature of inter-
action between hydrogen molecules and CNTs involved
physisorption (van der Waals interaction) and it indicates that
bare CNTs are not an eligible material for hydrogen storage
[7e13]. Basically, the weak binding of hydrogen releases easily
at low temperatures, while the strong binding of hydrogen
requires high temperature to release. However, it has been
shown that the addition of metal species with CNTs enhances
the binding energy of hydrogen as well as the storage capacity
(than CNTs) via two processes namely, i. Providing multiple
sites for adsorption and, ii. Electron charge transfer between
metal and carbon atoms [14e17]. Moreover, the hydrogenated
CNT-metal complex systems are reported to be stable at room
temperature [14e16]. Chen et al. [18] have found a higher
binding energy of hydrogen in Li doped CNT (0.18 eV) than
undoped CNT (0.025 eV) using DFT calculations and Yang et al.
[19] have measured the hydrogen storage capacity of 2.5 wt.%
in Li doped CNTs experimentally. Lipson et al. [20] have dis-
cussed electrochemical loading of SWCNTs encapsulated by
thin Pd coating leading to a storage capacity of 8e12 wt.% in
ambient conditions. A maximum storage capacity of 2 wt.%
has been observed by Sankaran et al. [21] in boron substituted
CNTs. Hydrogen storage properties of multi-walled CNTs
(MWCNTs) impregnated with Ni nanoparticles showed a high
hydrogen uptake upto 2.8 wt.% under moderate temperature
and pressure condition [22]. Rather et al. [23] have observed a
maximum reversible hydrogen storage capacity of 0.18 wt.% at
298 K and 1.6 MPa in pd embedded CNTs, which is nearly twice
the storage capacity of pristine CNTs. Shelvin et al. [14] have
performed ab initio DFT simulations on hydrogen storage in
CNT (8, 0) via defect-modulated titanium doping and reported
a high hydrogen storage capacity of 7.1 wt.%. The Pt dispersed
single-walled CNTs (SWCNTs) prepared by Reddy and Ram-
aprabhu [24] have showed an enhanced hydrogen uptake upto
3.03 wt.% at 125 K and 78 bar when compared to as-grown and
purified SWCNTs. Reyhani et al. [15] have compared the
hydrogen storage capacities of pure and metal nanoparticles
(Ca, Co, Fe, Ni, and Pd) decorated MWCNTs and found increase
in storage capacity in metal decorated MWCNTs.
The complexity with light elements such as Li, Be, B, Na
and Al is that the hydrogen bind either strongly (covalent or
ionic interactions) or weakly (van der Waals interactions) to
the host material [28]. The metals such as Pt, Pd and Ti are the
most investigated candidates to enhance the hydrogen stor-
age capacity of CNTs [23e27]. Among them, the heavy tran-
sition metals Pt and Pd are not good candidates for the
molecular absorption, because these metals showed the for-
mation of classical metal hydride cluster (PtH4, PdH4), which
has not bound to the nanotubes [28]. Moreover, the Pd-CNT
shows the hydrogen storage capacities measured in experi-
ments to be typically w0.5 wt.%, depending on the storage
condition [23,25e27]. On the other hand, the light transition
14655
metal, Ti showed a storage capacity of 8 wt.%, which is higher
than Pt and Pd [29]. Moreover, the study of interaction be-
tween metals such as Au, Al, Fe, Ti, Ni and Pd and SWCNTs
has also denoted that Ti interact strongly with the sidewall of
nanotubes through the partial covalent bonding while the
other metals Au and Al interact weakly with SWCNTs through
van der Waals forces [30]. Hence, the combinations of Ti metal
with CNTs for hydrogen storage lead us for the present
investigation with high interest.
Thus, aim of the present study is focused on the investi-
gation of hydrogen storage in SWCNTs-Ti composite. The
electron beam (EB) evaporation technique is used to prepare
and hydrogenate the SWCNTs-Ti composite simultaneously
for the first time. EB evaporation is one of the widely used
techniques for the preparation of composites such as
MWCNT-SnO2 [31], MWCNT-WO3 [32] and SWCNT-SnO2 [33].
Hence, we have also used the EB evaporation technique. The
amount of hydrogen uptake, desorption temperature range,
binding energy and the nature of hydrogen binding are dis-
cussed based on the characterization results.
2. Experimental
2.1. Materials preparation
SWCNTs were purchased from Sigma Aldrich with >98% pu-
rity. The Ti metal powder with >99% assay was purchased
from Merck. The expected amorphous carbon and metal im-
purities present in the purchased SWCNTs were removed by
the standard heating and acid washing procedures. Glass
substrates of dimension 25  75  1.35 mm3 were cleaned with
chromic acid, acetone and distilled water by means of soni-
cation for 30 min. SWCNTs were mixed with Ti metal powder
in the ratio of 1:2 by weight and ground well for 30 min using
an agate mortar. The mixture was placed in a cylinder-shaped
steel mould and an uni-axial pressure of 4e5 MPa was applied
to make them into tablet. Tablet with the diameter of 15 mm
and a height of 5 mm was obtained.
2.2. Composite preparation
The tablet was placed in water cooled graphite crucible and
then evaporated in hydrogen atmosphere by electron beam
(Hind Hivac Model-12A4D) on glass substrates. The substrates
were kept at a distance of 20 cm from the electron beam
source. The chamber base pressure was 5  106 mbar. The
vacuum chamber was flushed with hydrogen gas several
times before evaporation. A beam voltage of 6 kV with the
beam current of 30 mA was applied. The hydrogen gas was
allowed into the chamber till the pressure reduced to
5  105 mbar. The duration of evaporation was 15 min.
2.3. Hydrogenation
The hydrogen gas allowed through a regulated valve got
atomized by thermal cracking produced by the tungsten fila-
ment in the deposition unit [33,34]. The atomized and excited
molecules of hydrogen impinged on the substrates along with
the evaporant and thereby ensure the complete
14656 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0
hydrogenation process. The process of hydrogenation has
been done during the preparation of hydrogen storage me-
dium (composite) itself. The SWCNTs-Ti composite was pre-
pared and hydrogenated simultaneously in this way. In
addition to that, Ti was also prepared and hydrogenated under
same experimental conditions for the comparison study.
2.4. Characterization
The morphology of SWCNTs was analyzed by transmission
electron microscopy (TEM) using JEOL JEM 2100 model unit
with an accelerating voltage of 200 kV. Atomic force micro-
scopy (AFM) image of Ti thin film was obtained using A-100
SGS unit. X-ray diffraction (XRD) study was performed on
XPERT-PRO diffractometer operating at 40 kV and 30 mA,
using Cu Ka radiation. Scanning electron microscopy (SEM)
and the corresponding energy dispersive X-ray spectrum
(EDS) of SWCNTs-Ti composite was recorded using JEOL-
MODEL 6390 unit with an accelerating voltage of 5 kV.
Raman measurements were carried out in Renishaw InVia
model spectrometer with the laser excitation of 514 nm. CHN-
elemental analysis was performed to measure the amount of
hydrogen stored in hydrogenated Ti and SWCNTs-Ti com-
posite using Elementar Vario EL III model analyzer. The
thermo gravimetric/thermal desorption spectroscopy (TG/
TDS) measurements were carried out using Perkin
ElmereDiamond model unit over the temperature range of
40e800
C at a scanning rate of 10
C/min.
3. Results and discussion
3.1. Morphology studies
The TEM image of SWCNTs is shown in Fig. 1. The average
diameter of SWCNTs is estimated to be around 2e4 nm. AFM
image of Ti thin film shown in Fig. 2(a) reveals the formation of
titanium clusters as grains with various sizes in the range of
100e300 nm. Fig. 2b shows the XRD pattern of Ti thin film. The
Fig. 1 e TEM image of SWCNTs.
appeared typical peaks attributed to (100), (002) and (101) dif-
fractions. XRD data reveal the polycrystalline nature of Ti thin
film [35]. The additional peak along with Ti may be appeared
due to the formation of oxide in Ti thin film which is also
observed in the XRD pattern (unassigned peak). Fig. 3(a) shows
the SEM image of SWCNTs-Ti composite. The presence of
SWCNTs (indicated by the circles) along with Ti clusters in the
composite is confirmed from this SEM image together with the
corresponding EDS spectrum displayed in Fig. 3(b). The pres-
ence of elements in the SWCNTs-Ti composite is confirmed by
this study. Thus, the results reveal that the deposition of CNTs
with Ti is possible using EB evaporation technique without
any structural deformation of CNTs.
3.2. Hydrogen uptake studies
CHN-elemental analysis was carried out to measure the
amount of hydrogen incorporated in Ti and SWCNTs-Ti com-
posite. This is one of the widely used techniques for the mea-
surement of hydrogen storage and elements such as carbon,
hydrogen and nitrogen [2,33,36e38]. The amount of hydrogen
stored by the systems Ti and SWCNTs-Ti composite are found
to be 2.2 and 4.74 wt.%, respectively. In comparison with Ti, the
hydrogen uptake of SWCNTs-Ti composite has been signifi-
cantly enhanced and it is due to the cumulative adsorption of
hydrogen by CNTs and Ti constituents in the composite.
Hence, one can confirm that the synergistic effect existing
between CNTs and Ti nanostructures. From Figs. 2a and 3a, the
formation of Ti clusters is observed; this might have limited the
higher hydrogen uptake. The possible reason for this limitation
is that the Ti atoms residing inside the clusters cannot
contribute to hydrogen adsorption. Sun et al. [28] have also
pointed out that the clustering of Ti atoms on C60 surface could
reduce the storage capacity of the carbon nanostructures.
The Raman spectra of SWCNTs, SWCNTs-Ti composite and
hydrogenated SWCNTs-Ti composite is shown in Fig. 4.
Generally, the disordered (D) and graphitic (G) bands are the
two characterization bands for CNTs. The D band is typically
observed in the range of 1300e1400 cm1, and it is appeared
due to the presence of amorphous or disordered carbon in
CNTs. The most intensive tangential (G) mode is the high-
energy mode of SWCNTs, which normally exists in the range
of 1565e1595 cm1. The G band arises from in-plane tangen-
tial stretching of CeC bonds in CNTs which appeared due to
the displacement of carbon atoms in the circumferential di-
rection [5]. In the spectra of all the samples, the two bands
namely D and G appeared in their corresponding range.
Raman band for titanium metal did not appear in the spectra,
because it does not have Raman-active vibration modes [39].
Generally in Raman spectrum, the intensity ratio of D to G
band is a sign of defect/amorphous carbon concentration in
CNTs. The lesser D/G intensity ratio of 0.15 for SWCNTs in-
dicates the presence of lesser amount of defect/amorphous
carbon concentration in CNTs. Though Ti is Raman inactive,
the appearance of D, G peaks and increase in D/G ratio (0.33) of
the composite sample confirms the presence of SWCNTs in
the composite and the formation of composite, respectively.
After hydrogenation, the D band intensity has increased and
the corresponding G band intensity has decreased. The
 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0 14657

Fig. 2 e (a) AFM image, (b) XRD pattern of Ti thin film.

Fig. 3 e (a) SEM image, (b) EDS spectrum of SWCNTs-Ti composite.

corresponding D/G ratio has increased due to the increase in
defect density in the sample [5].
3.3. Desorption studies
In order to explore the mechanism of hydrogen storage,
we performed thermo gravimetric/thermal desorption
spectroscopy (TG/TDS) studies. Fig. 5 shows the thermo
gravimetric plot of hydrogenated Ti sample. For this sample,
the desorption of hydrogen starts at 230
C and ends at 310
C
and the corresponding weight loss in that region is about 2.2%.
The binding energy of hydrogen with Ti is calculated using
van’t Hoff equation [40] for the desorption temperatures 230,
275 and 310
C and the values are found to be 0.39, 0.43 and

Fig. 4 e Raman spectra of SWCNTs, SWCNTs-Ti composite Fig. 5 e Thermo gravimetric spectrum of hydrogenated Ti
and hydrogenated SWCNTs-Ti composite. sample.
14658 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0
0.46 eV. The activation energies of desorption of hydrogen [41]
are calculated to be 28.4, 31.7 and 34.4 kJ/mol for the corre-
sponding above mentioned desorption temperatures.
On the other hand, the thermo gravimetric plot of hydro-
genated SWCNTs-Ti composite displayed in Fig. 6(a) shows the
hydrogen desorption of about 4.74 wt.% in the temperature
range of 160e310
C. The binding energy of hydrogen with the
composite is calculated for the desorption temperatures 160,
243 and 310
C and the values are 0.34, 0.4 and 0.46 eV. The
activation energies of desorption of hydrogen are 23.4, 29.4 and
34.4 kJ/mol for the corresponding desorption temperatures.
The stored hydrogen has the weakest binding strength of
0.34 eV, which is much higher than van der Waals interactions.
It is worth mentioning that, both the hydrogenated samples
maintain its stability at room temperature. The desorption
spectrum of hydrogen (Fig. 6(b)) seems to be asymmetric
because of the existence of hydrogen with different bond
strengths offered by Ti and CNTs with various diameters in the
composite. From Fig. 6(c), it is clear that the entire (100%) stored
hydrogen is released approximately in a duration of 8 min. The
duration of desorption can be controlled by the ramp (scanning
rate) of the applied desorption temperature. It is inferred that
Fig. 6 e (a) Thermo gravimetric spectrum of hydrogenated SWCNTs-Ti composite, (b) Hydrogen desorption, (c) Time vs Mass
loss spectrum of hydrogenated SWCNTs-Ti composite.
the thermo gravimetric analysis together with CHN-elemental
analysis provides evidence for the measurement of hydrogen
storage in the designed system [33].
Yildirim et al. [29] have reported the simulation studies of
hydrogen storage on (8, 0) SWCNT decorated with Ti metal
atoms. A single Ti atom adsorbed on SWCNT strongly bound
upto four hydrogen molecules that lead to the storage capacity
of 8 wt.%. The first H2 adsorption was dissociative with the
binding energy of 0.83 eV, in which the metal atom becomes
metal hydride while the other three adsorptions are molecu-
lar. Experimentally, the hydrogenation of CNTs supported by
Pd/Ni metal particles also shows the formation of Pd/Ni hy-
dride [42]. Moreover, it is reported that the activation energies
for dehydrogenation of TiH2 to TiH and TiH to Ti are 74.79 and
131.92 kJ/mol, respectively [43]. While considering the binding
energy of hydrogen as well as activation energies for dehy-
drogenation of the present case, it does not show very much
strong binding of hydrogen with Ti as well as in the composite
samples. Hence, the stored hydrogen might be in molecular
state on both the samples. One of the possible reasons for this
kind of adsorption is that, during the process of incorporation
of hydrogen (evaporation), initially the H atoms have lower
 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0
coverage on the substrate (along with the composite). Further
the time of evaporation increases, the coverage of H atoms on
the substrate also increases (i.e. the available H atoms start to
incorporate on the neighboring sites on the composite and
this process continues up to higher coverage). This may lead
to the formation of hydrogen molecules upon higher coverage
[33]. During the course of desorption, the adsorbed H2 mole-
cules get desorbed molecularly. Another possible reason may
be the general spillover mechanism; one can expect this effect
in the presence of metal clusters networked with high surface
area materials like SWCNTs. On the process of evaporation,
the Ti metal may migrate the dissociated hydrogen atoms to
the nearest vacant sites on CNTs. During desorption, the
adsorbed hydrogen atoms were supposed to be recombined
into molecular hydrogen (reverse spillover) and get desorbed
[44]. This kind of adsorption of hydrogen needed a tempera-
ture range of 250e300
C to release the hydrogen [45,46]. The
desorption temperature range of hydrogen observed in this
work is in agreement with those reports. Therefore, spillover
mechanism may also contribute to hydrogenation and dehy-
drogenation of the composite. Besides, both of our samples
investigated here show 100% desorption. Thus, the adsorbed
hydrogen likely to be weakly chemisorbed in both of the
samples. The dispersion of CNTs in the composite leads to
more than one-fold increase of hydrogen uptake than Ti,
because this enables the maximum amount of contact be-
tween CNTs and hydrogen. Comparing the storage capacities
of the two systems, we propose that more than half of the
hydrogen is adsorbed by CNTs in the composite. Nikitin et al.
[47] have hydrogenated the SWCNT films using atomic
hydrogen. They have observed the hydrogen desorption in the
temperature range between 200 and 300
C, and noted that the
chemisorbed hydrogen (CeH) desorbs from the surface of
SWCNT. Here, our composite system shows the desorption of
hydrogen in the temperature range of 160e310
C. Hence, one
can emphasize that the stored hydrogen associated with CNTs
may have the attachment on its surface. Furthermore, it is
suggested that an ideal hydrogen storage medium should
have the binding energy of hydrogen in the range, 0.2e0.4 eV
[48]. Here, the average binding energy of hydrogen on the
composite is 0.4 eV. This in turn confirms the weak chemi-
sorption of hydrogen on the composite. In this binding energy
range the interaction between the host material and hydrogen
molecules is primarily due to the combination of electrostatic,
inductive and covalent charge transfer mechanisms [48,49].
Based on the investigation, one can conclude that the
composite materials containing SWCNTs and Ti nano-
structures having the ability of hydrogen uptake and the
achieved hydrogen uptake is due to the cumulative adsorption
of these materials and the method of preparation. Though, the
hydrogen uptake obtained here is close to the target of US DOE
for 2015, there is a scope (by avoiding the formation of clus-
tering of Ti atoms) of improving the hydrogen uptake further
on this SWCNTs-Ti composite.
4. Conclusion
In summary, we have investigated the hydrogen storage per-
formance of SWCNTs-Ti metal composite. The deposition of
14659
SWCNTs with Ti has been done successfully using EB evapo-
ration technique. The preparation of hydrogen storage me-
dium (composite) and the process of hydrogenation have been
done simultaneously using EB technique. The amount of
hydrogen uptake by the composite is found to be 4.74 wt.%,
and the adsorbed hydrogen are likely to be weakly chem-
isorbed on the composite. More than half of the hydrogen
(50%) is adsorbed by CNTs in the composite and the hydro-
genated samples are stable at room temperature. The hydro-
genated SWCNTs-Ti metal composite shows 100% desorption
in the temperature range of 160e310
C and the average
binding energy of hydrogen is found to be 0.4 eV. Based on the
investigation, it is inferred that the SWCNTs-Ti composite has
the potential of hydrogen storage for future applications.
Acknowledgments
The authors thank Madurai Kamaraj University (MKU), Uni-
versity Grants Commission (UGC), Council of Scientific and
Industrial Research (CSIR), and Sri Ramaswamy Memorial
(SRM) University. Dr. Suguna Shanmugasundaram, Head,
Department of Microbial Gene Technology, MKU is acknowl-
edged with thanks for AFM image. The authors thank Dr. T.R.
Ravindran, Scientific officer, Indira Gandhi Centre for Atomic
Research (IGCAR), Kalpakkam for Raman spectra.
references
[1] Ang SMC, Fraga ES, Brandon NP, Samsatli NJ, Brett DJL. Fuel
cell systems optimization-Methods and strategies. Int J
Hydrogen Energy 2011;36:14678e703.
[2] Silambarasan D, Surya VJ, Vasu V, Iyakutti K. Experimental
investigation of hydrogen storage in single walled carbon
nanotubes functionalized with borane. Int J Hydrogen Energy
2011;36:3574e9.
[3] Surya VJ, Iyakutti K, Rajarajeswari M, Kawazoe Y.
Functionalization of single-walled carbon nanotube with
borane for hydrogen storage. Phys E 2009;41:1340e6.
[4] Liu C, Chen Y, Wu C-Z, Xu S-T, Cheng H-M. Hydrogen storage
in carbon nanotubes revisited. Carbon 2010;48:452e5.
[5] Silambarasan D, Vasu V, Surya VJ, Iyakutti K. Investigation of
hydrogen desorption from hydrogenated single-walled
carbon nanotubes functionalized with borane. IEEE Trans
Nanotechnol 2012;11:1047e53.
[6] Dillon AC, Jones KM, Bekkendahl TA, Kiang CH, Bethune DS,
Heben MJ. Storage of hydrogen in single-walled carbon
nanotubes. Nature 1997;386:377e9.
[7] Rzepka M, Lamp P. Physisorption of hydrogen on
microporous carbon and carbon nanotubes. J Phys Chem B
1998;102:10894e8.
[8] Ye Y, Ahn CC, Witham C, Fultz B, Liu J, Rinzler AG, et al.
Hydrogen adsorption and cohesive energy of single-walled
carbon nanotubes. Appl Phys Lett 1999;74:2307e9.
[9] Arellano JS, Molina LM, Rubio A, Lo’pez MJ, Alonso JA.
Interaction of molecular and atomic hydrogen with (5,5) and
(6,6) single-wall carbon nanotubes. J Chem Phys
2002;117:2281e8.
[10] Cabria I, Lo’pez MJ, Alonso JA. Density functional study of
molecular hydrogen coverage on carbon nanotubes. Comput
Mater Sci 2006;35:238e42.
14660 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 8 ( 2 0 1 3 ) 1 4 6 5 4 e1 4 6 6 0
[11] Sudan P, Zuttel A, Mauron P, Emmenegger C, Wenger P,
Schlapbach L. Physisorption of hydrogen in single-walled
carbon nanotubes. Carbon 2003;41:2377e83.
[12] Henwood D, Carey JD. Ab initio investigation of molecular
hydrogen physisorption on graphene and carbon nanotubes.
Phys Rev B 2007;75:245413e22.
[13] Tibbetts GG, Meisner GP, Olk CH. Hydrogen storage capacity
of carbon nanotubes, filaments, and vapor-grown fibers.
Carbon 2001;39:2291e301.
[14] Shevlin SA, Guo ZX. High-capacity room-temperature
hydrogen storage in carbon nanotubes via defect-modulated
titanium doping. J Phys Chem C 2008;112:17456e64.
[15] Reyhani A, Mortazavi SZ, Mirershadi S, Moshfegh AZ,
Parvin P, Nozad Golikand A. Hydrogen storage in decorated
multiwalled carbon nanotubes by Ca, Co, Fe, Ni, and Pd
nanoparticles under ambient conditions. J Phys Chem C
2011;115:6994e7001.
[16] Gao L, Yoo E, Nakamura J, Zhang W, Chua HT. Hydrogen
storage in PdeNi doped defective carbon nanotubes through
the formation of CHx (x ¼ 1, 2). Carbon 2010;48:3250e5.
[17] Liu W, Zhao YH, Li Y, Jiang Q, Lavernia EJ. Enhanced
hydrogen storage on Li-dispersed carbon nanotubes. J Phys
Chem C 2009;113:2028e33.
[18] Chen L, Zhang YM, Koratkar N, Jena P, Nayak SK. First
principles study of interaction of molecular hydrogen with
Li-doped carbon nanotube peapod structures. Phys Rev B
2008;77:033405e8.
[19] Yang RT. Hydrogen storage by alkali-doped carbon
nanotubes-revisited. Carbon 2000;38:623e6.
[20] Lipson G, Lyakhov BF, Saunin EI, Tsivadze AY. Evidence for
large hydrogen storage capacity in single-walled carbon
nanotubes encapsulated by electroplating Pd onto a Pd
substrate. Phys Rev B 2008;77:081405e9.
[21] Sankaran M, Viswanathan B. Hydrogen storage in boron
substituted carbon nanotubes. Carbon 2007;45:1628e35.
[22] Kim H-S, Lee H, Han K-S, Kim J-H, Song M-S, Park M-S, et al.
Hydrogen storage in Ni nanoparticle-dispersed multiwalled
carbon nanotubes. J Phys Chem B 2005;109:8983e6.
[23] Rather S, Zacharia R, Hwang SW, Naik M, Nahm KS.
Hydrogen uptake of palladium-embedded MWCNTs
produced by impregnation and condensed phase reduction
method. Chem Phys Lett 2007;441:261e7.
[24] Reddy ALM, Ramaprabhu S. Hydrogen adsorption properties
of single-walled carbon nanotube-nanocrystalline platinum
composites. Int J Hydrogen Energy 2008;33:1028e34.
[25] Dag S, Ozturk Y, Ciraci S, Yildirim T. Adsorption and
dissociation of hydrogen molecules on bare and
functionalized carbon nanotubes. Phys Rev B 2005;72:8.
155404.
[26] Lueking AD, Yang RT. Hydrogen spillover to enhance
hydrogen storage-study of the effect of carbon
physicochemical properties. Appl Catal A Gen
2004;265:259e68.
[27] Yang FH, Lachawiec AJ, Yang RT. Adsorption of spillover
hydrogen atoms on single- wall carbon nanotubes. J Phys
Chem B 2006;110:6236e44.
[28] Sun Q, Wang Q, Jena P, Kawazoe Y. Clustering of Ti on a C60
surface and its effect on hydrogen storage. J Am Chem Soc
2005;127:14582e3.
[29] Yildirim T, Ciraci S. Titanium-decorated carbon nanotubes
as a potential high-capacity hydrogen storage medium. Phys
Rev Lett 2005;94:4. 175501.
[30] Zhang Y, Franklin NW, Chen RJ, Dai H. Metal coating on
suspended carbon nanotubes and its implication to metal-
tube interaction. Chem Phys Lett 2000;331:35e41.
[31] Wisitsoraat A, Tuantranont A, Thanachayanont C,
Patthanasettakul V, Singjai P. Electron beam evaporated
carbon nanotubes dispersed SnO2 thin film gas sensor. J
Electroceram 2006;17:45e9.
[32] Madhusudhana H, Chanodrkar N. Response study of electron
beam evaporated thin-film tin oxide gas sensors. Sens
Actuators 1992;B9:1e8.
[33] Silambarasan D, Surya VJ, Vasu V, Iyakutti K. One-step
process of hydrogen storage in single walled carbon
nanotubes-tin oxide nano composite. Int J Hydrogen Energy
2013;38:4011e6.
[34] Eibl C, Lackner G, Winkler A. Quantitative characterization of
a highly effective atomic hydrogen doser. J Vac Sci Technol A
1998;16:2979e89.
[35] Song Y-H, Cho SJ, Jung CK, Bae IS, Boo J-H. The structural
and mechanical properties of Ti films fabricated by using
RF magnetron sputtering. J Korean Phys Soc
2007;51:1152e5.
[36] Subrahmanyam KS, Kumar Prashant, Maitra Urmimala,
Govindaraj A, Hembram KPSS, Waghmare UV, et al.
Chemical storage of hydrogen in few-layer graphene. PNAS
2011;108:2674e7.
[37] Sankaran M, Viswanathan B. Nitrogen-containing carbon
nanotubes as a possible hydrogen storage medium. Indian J
Chem 2008;47:808e14.
[38] Badzian A, Badzian T, Breval E, Piotrowski A.
Nanostructured, nitrogen-doped carbon materials for
hydrogen storage. Thin Solid Films 2001;398e399:170e4.
[39] Lohse BH, Calka A, Wexler D. Raman spectroscopy as a tool
to study TiC formation during controlled ball milling. J Appl
Phys 2005;97:7. 114912.
[40] Durgun E, Ciraci S, Yildirim T. Functionalization of carbon-
based nanostructures with light transition-metal atoms for
hydrogen storage. Phys Rev B 2008;77:9. 085405.
[41] Ioannatos GE, Verykios XE. H2 storage on single- and multi-
walled carbon nanotubes. Int J Hydrogen Energy
2010;35:622e8.
[42] Jianwei R, Shijun L, Junmin L. Hydrogen storage of
multiwalled carbon nanotubes coated with PdeNi
nanoparticles under moderate conditions. Chin Sci Bull
2006;51:2959e63.
[43] Bhosle V, Baburaj EG, Miranova M, Salama K.
Dehydrogenation of TiH2. Mater Eng A 2003;356:190e9.
[44] Li YW, Yang FH, Yang RT. Kinetics and mechanistic model
for hydrogen spillover on bridged metal-organic frameworks.
J Phys Chem C 2007;111:3405e11.
[45] Contescu CI, Brown CM, Liu Y, Bhat VV, Gallego NC.
Detection of hydrogen spillover in palladium-modified
activated carbon fibers during hydrogen adsorption. J Phys
Chem C 2009;113:5886e90.
[46] Campesi R, Cuevas F, Gadiou R, Leroy E, Hirscher M, Vix-
Guterl C, et al. Hydrogen storage properties of Pd nanoparticle/
carbon template composites. Carbon 2008;46:206e14.
[47] Nikitin A, Li X, Zhang Z, Ogasawara H, Dai H, Nilsson A.
Hydrogen storage in carbon nanotubes through the
formation of stable CeH bonds. Nano Lett 2008;8:162e7.
[48] Lochan RC, Head-Gordon M. Computational studies of
molecular hydrogen binding affinities: the role of dispersion
forces, electrostatics, and orbital interactions. Phys Chem
Chem Phys 2006;8:1357e70.
[49] Surya VJ, Iyakutti K, Venkataramanan NS, Mizuseki H,
Kawazoe Y. Single walled carbon nanotubes functionalized
with hydrides as potential hydrogen storage media: a survey
of intermolecular interactions. Phys Status Soildi B
2011;248:2147e58.