Journal of Solid State Chemistry 190 (2012) 126129

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Journal of Solid State Chemistry

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

First-principles study of hydrogen storage on Ti-decorated B2C sheet

Y.H. Guo, B. Xu, Y.D. Xia, J. Yin, Z.G. Liu n
Department of Materials Science and Engineering and National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China

a r t i c l e i n f o a b s t r a c t

Article history: The hydrogen storage capacity of Ti decorated B2C sheet has been investigated by rst-principles plane-
Received 23 November 2011 wave calculation. It is revealed that a single Ti atom adsorbed on the B2C sheet can strongly bind up to
Received in revised form four hydrogen molecules. The adsorption energy is in the range of  0.36  0.82 eV/H2, which is
5 February 2012
suitable for ambient temperature hydrogen storage. Considering the fact that Ti can be loaded on both
Accepted 12 February 2012
Available online 21 February 2012
sides of B2C sheet, corresponding gravimetric storage capacity of Ti/B2C system was also calculated and
it can reach to about 7.0 wt%, exceeding the minimum requirement of 6.0 wt% for applications.
Keywords: & 2012 Elsevier Inc. All rights reserved.
Hydrogen storage
Binding mechanism
Adsorption energy
B2C sheet

1. Introduction fundamentally proportional to the specic surface area and the

Hydrogen gas, with advantages of high heat value, rich
resources and non-pollution, has been considered as the optimal
candidate in an economy based on renewable resources [1].
However, the safe storage and efcient transport of hydrogen
gas was a crucial target in the development of hydrogen economy
[2,3]. Great efforts have been made to nd materials that can
store hydrogen reversibly with high gravimetric and volumetric
density and operate under moderate temperatures and pressures.
Moreover, the U.S. Department of Energy (DOE) proposed goals,
such as the H2 capacity should exceed 6.0 wt%, and the adsorption
energy should be between 0.20 and 0.70 eV/H2 [4].
In the past decades, more and more attention has been focused
on the carbon-based nanostructure materials, such as carbon
nanotubes (CNTs), fullerenes and graphenes. Due to their high
surface-to-bulk ratio, these nanomaterials appear to be possible
candidate structures for hydrogen storage [57]. Unfortunately, it
was established that the interaction between hydrogen molecule
and bare CNT or graphite sheet is too weak for hydrogen storage
at ambient conditions [8]. In contrast, the introduction of transi-
tion metal (TM) to the pure carbon nanomaterials has been
proposed to enhance the hydrogen-uptake capacity and the
adsorption energy [916]. It was reported that a single Ti atom
adsorbed on (8, 0) single-wall carbon nanotube can adsorb up to
four hydrogen molecules, reaching to gravimetric storage capacity
of  8 wt% [9]. Clearly, the hydrogen storage capacity is
n
Corresponding author. Fax: 86 25 83595535.
E-mail address: liuzg@nju.edu.cn (Z.G. Liu).
number of dispersed metal atoms.
Recently, the boron-based materials, such as BN nanotubes
[17,18], BN sheet [19] and BC3 [20] have been proposed as the
host materials in order to avoid metal clustering. Interestingly, it
is reported that like carbon, the boron carbon complex may be
used to construct graphene sheet, nanotubes or nanoribbons
according to theoretical calculations [21]. Due to the introduction
of lighter elements in boroncarbon complex, one can image that
the boroncarbon materials might enhance the hydrogen storage
capacity in gravimetric density, as compared with the carbon-
based materials. More recently, H. An and co-workers reported
that Li-doped B2C graphene can serve as a high-capacity hydrogen
storage medium with the gravimetric density of 7.54 wt% [22].
Considering that Ti-decorated B2C is much more stable in the
atmosphere and water vapor as compared with Li-doped B2C, we
report a rst-principles computation of the interaction between
hydrogen molecules and Ti atoms adsorbed B2C sheet. Our
calculations showed that Ti-decorated on both sides of B2C sheet
can store up to 7.0 wt% of hydrogen in molecule form, which meet
the need of the DOE target.
2. Method of calculation
Our results have been obtained by using the spin-polarized
rst-principles calculations as implemented in the Vienna
Ab-initio Simulation Package (VASP) [23].The generalized gradi-
ent approximation (GGA) in the form of the PBE-type [24]
parameterization is employed for the exchange of electrons. The
ionic pseudo-potentials are described via the projector-augmen-
ted wave (PAW) method [25], and the cutoff energy for the

0022-4596/$ - see front matter & 2012 Elsevier Inc. All rights reserved.
doi:10.1016/j.jssc.2012.02.032
 Y.H. Guo et al. / Journal of Solid State Chemistry 190 (2012) 126129
plane-wave basis is set as 400 eV. To model the interaction of
hydrogen molecules with the B2C sheet, a 12-atom supercell
(2  2 unit cells) was used to simulate an innite sheet. The
interlayer distance was set to be 15 A, which is enough to
minimize the articial interlayer interactions. The Brillouin zone
was sampled by 6  4  1 special mesh points in K space based on
MonkhorstPack scheme. Atomic positions in all structures are
fully relaxed by employing the conjugate-gradient (CG) algo-
rithm. The relaxations are assumed to be complete when the
total energy difference between the last two consecutive steps is
less than 10  5 eV and the maximum force allowed on each atom
is less than 10  2 eV/A.
3. Results and discussions
3.1. Structural study and storage ability analysis
As a starting point, the geometry properties of B2C sheet are
recalculated. Based on our calculations, it is found that the
optimized parameters of B2C sheet obtained by energy minimiza-
tion are a2.558 A and b3.435 A, in good agreement with that in
Ref. [21](a2.558 A and b3.453 A). Next, we consider the adsorp-
tion of a single Ti atom on the B2C sheet. Fig. 1(a) shows the ve
possible adsorption sites on the B2C sheet, involving two top sites (C
or B), the hexagonal hollow site, the rhombuses hollow site and the
bridge site. The binding energies of a single Ti atom at these sites
are given in Fig. 1(b). After a full relaxation, it is found that the
preferable conguration is on the hexagonal hollow site, at which
the Ti atom seated at the center of the hexagon with about 1.64 A
above the B2C sheet. Its binding energy is calculated to be
3.48 eV. Here, the binding energy for the single Ti atom is dened
as Eb E(Ti/B2C)-E(B2C)-E(Ti), in terms of the total energy of the B2C
sheet with Ti absorption E(Ti/B2C), the pristine B2C sheet and the
free Ti atom. The binding energy of the Ti atom at the top of B site
and the bridge site is about 0.16 and 0.22 eV higher in energy, as
compared with the hexagonal hollow site, respectively. The Ti atom
at the rhombuses hollow site and the top of C site are unstable. The
initial Ti atom located at the rhombuses hollow site will relax to the
top of B site, while Ti at the top of C will move into hexagonal site
without any energy barrier. In order to nd the nature of electronic
properties of Ti on B2C sheet, we give the atomic projected density
of states (PDOS) shown in Fig. 2. In fact, the metals are much easier
to donate their s electrons to B2C sheet due to their relatively low
ionization potentials. The donated electrons partially ll the unoc-
cupied states of B2C sheet as indicated by the PDOS near Fermi
level. On the other hand, there is a nite probability for B2C sheet to
back donate part of its received electrons from the metal atoms to
their low-lying d orbitals, resulting in a strong hybridization
Fig. 1. Various adsorption sites of a single Ti atom adsorbed on the (2  2) cell of
B2C sheet: A top site of C atom; B top site of B atom; C hexagonal hollow site; D
rhombuses hollow site; E bridge site. The relevant binding energies at these sites
are given in (b). The pink and gray atoms are B and C, respectively.
127
Fig. 2. The density of states (DOS) of pure B2C sheet and projected density of
states (PDOS) Ti on B2C sheet.
between Ti and B2C sheet. Such a strong hybridization can be
appreciated from the resonated peak in PDOS near the Fermi level
as shown in Fig. 2. This strong hybridization stabilized the adstoms
and prevented them from clustering. Moreover, we have performed
a further calculation with two Ti atoms in a 2  2 unit cell of B2C
sheet. The results showed that agglomeration of Ti atoms to form
cluster should overcome an energy barrier about 1.4 eV. It is so
large that the Ti atoms prefer to stay at the hollow site rather than
to form clusters on the B2C surface.
Based on the optimal structure described above, we then
investigated the H2 storage capacity by considering different
number of hydrogen molecules adsorbed on the Ti/B2C complex.
We added hydrogen molecules around the Ti adatom one by one,
and then fully optimized their geometries without symmetry
connement. For each number of hydrogen molecules on Ti/B2C
complex, tens of possible initial congurations were constructed. As
shown in Fig. 3, we give the most favorable adsorption geometries
for every number of hydrogen molecules on Ti/B2C complex. It is
found that the hydrogen molecule prefers to aslant ride on the TiB
bond as shown in Fig. 3(a) for the single molecule on Ti/B2C
complex. The hydrogen molecule on the top of Ti atom in
Fig. 3(b) also stably sticks to Ti atom, but it is about 0.33 eV higher
in binding energy, unstable than conguration (a). For two hydro-
gen molecules on the Ti/B2C complex, the most stable conguration
is shown in Fig.3(c), in which the two hydrogen molecules lie on the
BB bond and bind to the Ti atom. The conguration with hydrogen
molecules along the TiC bond as shown in Fig. 3(d) has almost the
same energy as conguration (c). The most preferable conguration
for three hydrogen molecules binding to Ti/B2C complex is shown
in Fig. 3(e), in which two of them lie along the TiB bond and the
third one is on the shoulder of BB bond. Three energy-degenerated
congurations are shown in Fig. 3(f)(h). Their total energy is about
160 meV, higher than that of conguration (e). Interestingly, we
found that in the case of four hydrogen molecules, as shown in
Fig. 3(i), the hydrogen molecules well lie along the four Ti B bonds,
respectively, forming the most stable conguration. As compared
with conguration (i), the conguration (j) is unstable with an
increase in the binding energy of 0.45 eV. The detailed calculations
showed that additional hydrogen molecule can weakly bind to the
Ti atom from the top of it with the binding energy of about
 10 meV, and no more hydrogen molecules can be bound to the
Ti/B2C complex. The results revealed that like in the case of
Ti/graphene complex [26], each Ti atom placed on the B2C sheet
can adsorb up to four H2 molecules. The adsorption energy and the
128 Y.H. Guo et al. / Journal of Solid State Chemistry 190 (2012) 126129
Fig. 3. The most favorable adsorption geometries for different number of hydrogen molecules on Ti/B2C complex: (a), (b) one H2 molecule, (c), (d) two H2 molecules, (e),
(f), (g), (h) three H2 molecules and (i), (j) four H2 molecules. The pink atoms are B, the gray atoms are C, the blue atom is Ti and the white atoms are H.
Table 1
The adsorption energy and the average bond length of H2 molecule for different
number of the adsorbed H2 molecules.
Conguration Eb (eV/H2)
A  0.82
B  0.49
C  0.49
D  0.45
E  0.47
F  0.41
G  0.41
H  0.41
I  0.36
J  0.25
average bond length for the hydrogen molecule are listed in Table 1.
The adsorption energy of H2 molecule is calculated by using the
formula Ead(H2)(E(total)E(Ti/B2C))/nE(H2), with the total
energy E(total) for hydrogen molecule adsorbed on Ti/B2C complex,
E(Ti/B2C) for the Ti/B2C complex and E(H2) for the free standing
hydrogen molecule. From Table 1, we can nd that all the bond
indicating that all
lengths of HH are in the range of 0.8050.918 A,
the hydrogen remain the molecule form. And their adsorption
energies are in the range of  0.25 0.82 eV/H2, promising for
hydrogen adsorption and release at ambient conditions. The calcu-
lated hydrogen storage capacity is about 4.4 wt%. In order to further
enhance the hydrogen storage capacity, the B2C sheet decorated by
Ti from both sides was also calculated. It is concluded that the
adsorption energy remains 0.36 eV for four hydrogen molecule
binding to each Ti atom, while the hydrogen storage capacity have
reached to 7.0 wt%, satisfying the requirement set by DOE.
3.2. The PDOS and charge differences analysis
To understand the mechanism of hydrogen absorption, we
depicted the projected densities of states (PDOS) of Ti/B2C com-
plex holding (a) one single H2, (b) two H2, (c) three H2 and (d) four
H2 molecules in Fig. 4. For simplicity, only the PDOS of the most
stable congurations for different number of hydrogen molecules
on Ti/B2C complex are shown. The black solid lines, red solid lines
and the blue solid lines are for the PDOS of the B2C sheet, Ti atom
and hydrogen molecule, respectively. At rst glance, we can nd
that the 3d orbit of Ti atom is located at the range between 2 eV
and the Fermi level with a broad tail. This tail stems from the
interaction between Ti and B2C sheet through the so-called Dewar
interaction [27]. Ti atoms donate their s electrons to B2C sheet. At
the same time, the substrate will back donates part of its received
electrons from the metal atoms to the low-lying empty d orbital,
resulting in a strong hybridization between the p orbital of the
dHH (A)
B2C sheet and d orbital of Ti atom. The electron donation and back
0.918 donation mechanisms help considerably stabilize the chemical
0.829 interaction between Ti and B2C sheet. However, the s orbital of
0.865 hydrogen is located far below the Fermi level (ranging from  10
0.816  7 eV). As the energy difference between H s orbital and Ti d
0.817
orbital is so large, the binding mechanism can not be understood
0.823
0.827 in the frame of the hybrization between the Ti and H. This can be
0.805 proved by examining the charge difference with and without
0.822 hydrogen molecules adsorbed on Ti/B2C complex. As a typical
0.854
example, we give the charge difference shown in Fig. 5 for
conguration (c) and (i) in Fig. 3. The red isosurface in Fig. 5
describes the charge depletion while the blue isosurface depicts
the charge accumulation. Obviously, one can nd that the charge
density of hydrogen molecules transfers from the zone away from
Ti to the zone near Ti atoms. It should be noted that there is no
charge transfer between hydrogen and Ti atoms, indicating the
interaction between Ti and hydrogen is not due to the hybriza-
tion. This clearly shows that the hydrogen binding to Ti is
originated from its polarization under the electric eld introduced
by Ti atom. Hence the main interaction mechanism is the
electrostatic Coulomb attraction between Ti and hydrogen.
Moreover, one can nd that the hydrogen s orbital splits into
several peaks as shown in Fig. 4(c) and (d). The splitting of s
orbital of hydrogen indicates the interaction between the hydro-
gen molecules, indicating the formation of a super-hydrogen
molecule. This phenomenon is further conrmed by the charge
difference shown in Fig. 5(a) and (b) for two or four hydrogen
molecules absorbed on Ti/B2C complex. Clearly, charge depletes
from the HH bond and accumulates in the region between H2
molecules. Fig. 5(a) and (b) describe the charge density redis-
tribution, showing the formation of H2H2 bonds. The formation
of super-hydrogen molecule prevails for four hydrogen molecules
on Ti/B2C under the manipulation of the electric eld induced by
Ti atom. It is the formation of the super hydrogen molecule that
further lowers the hydrogen adsorption energy.
4. Conclusions
In summary, the behavior of hydrogen molecules adsorbed on
Ti/B2C complex has been investigated by using rst-principle
calculations. Our results showed that up to four hydrogen
 Y.H. Guo et al. / Journal of Solid State Chemistry 190 (2012) 126129 129

Fig. 4. Calculated projected DOS (PDOS) on H s (blue curve), B2C sheet (black curve) and Ti 3d (red curve) orbitals for most stable congurations of Ti/B2C complex holding
(a) one single H2, (b) two H2, (c) three H2 and (d) four H2 molecules.

the Priority Academic Program Development of Jiangsu Higher

Education Institutions (PAPD). Bo Xu wants to thank the support
by the China Postdoctoral Science Foundation funded project
(20100481119) and Jiangsu Planned Projects for Postdoctoral
Research Funds (1002007B). The calculations were performed
on the parallel computers at High Performance Computing Center
(HPCC) of Nanjing Univesrity.

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