Octagraphene as a versatile carbon atomic sheet for novel nanotubes,

unconventional fullerenes, and hydrogen storage

Xian-Lei Sheng, Hui-Juan Cui, Fei Ye, Qing-Bo Yan, Qing-Rong Zheng et al.

Citation: J. Appl. Phys. 112, 074315 (2012); doi: 10.1063/1.4757410

View online: http://dx.doi.org/10.1063/1.4757410
View Table of Contents: http://jap.aip.org/resource/1/JAPIAU/v112/i7
Published by the American Institute of Physics.

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 JOURNAL OF APPLIED PHYSICS 112, 074315 (2012)

Octagraphene as a versatile carbon atomic sheet for novel nanotubes,

unconventional fullerenes, and hydrogen storage
Xian-Lei Sheng,1 Hui-Juan Cui,1 Fei Ye,2 Qing-Bo Yan,2 Qing-Rong Zheng,1
and Gang Su1,a)
1
Theoretical Condensed Matter Physics and Computational Materials Physics Laboratory,
College of Physical Sciences, Graduate University of Chinese Academy of Sciences, Beijing 100049, China
2
College of Materials Science and Opto-Electronic Technology, Graduate University of Chinese Academy of
Sciences, Beijing 100049, China

(Received 1 May 2012; accepted 5 September 2012; published online 8 October 2012)
We study a versatile structurally favorable periodic sp2-bonded carbon atomic planar sheet with
C4v symmetry by means of the first-principles calculations. This carbon allotrope is composed of
carbon octagons and squares with two bond lengths and is thus dubbed as octagraphene. It is a
semimetal with the Fermi surface consisting of one hole and one electron pocket, whose low-
energy physics can be well described by a tight-binding model of p-electrons. Its Young’s
modulus, breaking strength, and Poisson’s ratio are obtained to be 306 N/m, 34.4 N/m, and 0.13,
respectively, which are close to those of graphene. The novel sawtooth and armchair carbon
nanotubes as well as unconventional fullerenes can also be constructed from octagraphene. It is
found that the Ti-absorbed octagraphene can be allowed for hydrogen storage with capacity around
C 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4757410]
7.76 wt. %. V

I. INTRODUCTION is more favorable in energy than graphyne and graphdiyne,

1 although it is metastable against graphene. By rolling octa-
The discovery of graphene opens a new era of funda-
graphene along specific directions, we can get novel saw-
mental research and technological applications of carbon-
tooth and armchair carbon nanotubes [Fig. 1(b)] that are
based materials. Graphene is an elegant two-dimensional (2D)
metallic, which can escape from the difficult separation of
material exhibiting exceptional electrical, thermal, mechani-
usual metallic and semiconducting carbon nanotubes;19 by
cal, and optical properties, and its low-energy behavior of
electrons is described by a (2 þ 1)-dimensional relativistic wrapping octagraphene and making use of pentagons, hexa-
quantum theory.2–4 Stimulated by the tremendous interest of gons, or heptagons as caps, many stable unconventional full-
graphene, a great number of novel carbon structures were pro- erenes such as C36, C48, C80, C96, and so forth [Fig. 1(c)] can
posed and investigated in the past years (e.g., Refs. 5–10). be constructed. The electronic properties of octagraphene
Among others, two intriguing sp-sp2-bonded monolayers of manifest that it is a semimetal with small density of states
elemental carbon, graphyne11 and graphdiyne,12,13 and an (DOS) around the Fermi level, whose Fermi surface consists
insulating 2D hydrocarbon layer, graphane,14,15 are typical of one hole and one electron pockets centered at C and M
examples, all of which were experimentally obtained. It points, respectively. The low-energy physics of octagraphene
appears that there is a growingly extensive interest to seek for can be well described by a tight-binding model of p elec-
more 2D allotropes of carbon with amazing physical and trons. Octagraphene has the density of 0.68 mg/m2, Young’s
chemical properties as well as possibly diverse applications. modulus of 306 N/m, breaking strength of 34.4 N/m, and
Graphene has a perfect honeycomb lattice with C6v sym- Poisson’s ratio of 0.13. It could be the strongest periodic car-
metry. Recent studies6,16,17 show that the line defects with bon sheet after graphene till now. An energy gap can be
octagons and pentagons could be formed self-assembly in opened by doping boron nitrogen pairs. The possible routes
graphene. The formation of small carbon molecules with var- for obtaining octagraphene are suggested. The Ti-absorbed
ious polygon rings has also been studied from experimental octagraphene can also be used for hydrogen storage with
aspects.18 Inspired by these observations, we propose a sta- capacity of 7.76 wt. %. With these amazing characters, we
ble 2D periodic atomic sheet consisting of carbon octagons, anticipate that octagraphene, similar to its cousin—graphene,
coined as octagraphene, which possesses intriguing proper- once being obtained, will likewise have a crucial impact in
ties and might be synthesized experimentally by line defects physics, chemistry, materials and information sciences.
or acetylene scaffolding ways. As shown in Fig. 1(a), octa- The rest of this article is organized as follows. In Sec. II,
graphene comprises of carbon octagons and squares with the calculational methods are described. In Sec. III, the geo-
two bond lengths that forms a square lattice with C4v symme- metrical structure, mechanical properties, electronic struc-
try. By means of the first-principles calculations, it is shown tures, and low-energy physics of octagraphene are presented.
that octagraphene is energetically and kinetically stable and In Sec. IV, new carbon nanotubes and unconventional fuller-
enes from octagraphene are given. The band engineering and
a)
Author to whom correspondence should be addressed. Electronic mail: hydrogen storage of octagraphene are discussed in Sec. V.
gsu@gucas.ac.cn. Finally, a conclusion is briefly presented.

0021-8979/2012/112(7)/074315/7/$30.00 112, 074315-1 C 2012 American Institute of Physics

V

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074315-2 Sheng et al. J. Appl. Phys. 112, 074315 (2012)

FIG. 2. (a) Cohesive energy per atom as a function of lattice constant a for
graphene, octagraphene, graphyne, and graphdiyne, respectively, where a0 is
the optimized lattice constant. (b) Phonon spectra of octagraphene.
A lattice constant is one of the physical dimensions and angles that determine the geometry of the unit cells in a
crystal lattice and is proportional to the distance between atoms in the crystal. A simple cubic crystal has only one
lattice constant, the distance between atoms, but in general lattices in three dimensions have six lattice constants: the
lengths a, b, and c of the three cell edges meeting at a vertex, and the angles , , and between those edges.
square lattice with the lattice constant a0 ¼ 3.45 Å, where a
unit cell contains four carbon atoms. Similar to graphene, ev-
FIG. 1. Schematic depiction of the structures of (a) octagraphene, where a unit
ery carbon atom in octagraphene has three sp2-bonded nearest
cell is indicated with the unit vectors a1 and a2; (b) single-wall sawtooth (10,0)
and armchair (8,8) carbon nanotubes rolled from octagraphene; and (c) uncon-
neighbors, forming three r bonds. In addition, octagraphene
ventional fullerenes of C36, C48, C80, and C96 obtained from octagraphene.
has two types of bond lengths, 1.48 Å of intra-squares and
1.35 Å of inter-squares, and two bond angles 90 and 135 .
II. CALCULATIONAL METHODS
The cohesive energy Ec per atom as a function of lattice
Both the first-principles calculations within the frame- constant (a/a0) is given in Fig. 2(a) for graphene, octagra-
work of the density-functional theory (DFT)20,21 and the tight- phene, graphyne, and graphdiyne, respectively. It is clear
to call on for protection or witness
binding approximation (TBA)22 are invoked to study this 2D that a single minimum of—Ec appears at a/a0 ¼ 1 for these
system. For the first-principles method, primary calculations 2D structures, suggesting that they are energetically stable.
were performed within the Vienna ab initio simulation pack- Note that the minimum of—Ec for octagraphene is smaller
age (VASP)23,24 with the projector augmented wave (PAW) than those of graphyne and graphdiyne but larger than that of
method.25 Both the local density approximation (LDA) in the graphene, suggesting octagraphene is more energetically sta-
form of Perdew-Zunger26 and generalized gradient approxi- ble than graphyne and graphdiyne but metastable against
mation (GGA) developed by Perdew and Wang27 were graphene. Fig. 2(b) gives the phonon spectra of octagra-
adopted for the exchange correlation potentials. The plane- phene. No imaginary phonon modes are found, implying that
wave cutoff energy is taken as 400 eV. The Monkhorst-Pack octagraphene is also kinetically stable. We performed quan-
scheme for k-point samplings with 32  32  1 mesh for pla- tum molecular dynamics simulations and found that at tem-
nar sheets and 1  1  100 mesh for nanotubes was used to perature 500 K, the planar structure of octagraphene still
sample the Brillouin zone.28 The supercells are used for calcu- maintains. Considering that graphyne and graphdiyne were
lations of isolated sheet structures, and the distance between already obtained experimentally, it is reasonable to believe
two layers is about 10 Å to avoid interactions. The geometries that octagraphene can be synthesized in lab or likely already
were optimized when the remanent Hellmann-Feynman forces exists in nature. In fact, carbon rings with four or eight sides
on the ions are less than 0.01 eV/Å. Phonon calculations with have already been observed in some experiments.16,17
a k-mesh of 8  8  1 are performed using the density func- For a comparison, the cohesive energy Ec, density q,
tional perturbation theory.29 bond length lCC, energy gap Eg, Young’s modulus E, breaking
strength r, and Poisson’s ratio  for graphene, octagraphene,
III. OCTAGRAPHENE graphyne, and graphdiyne, respectively, are collected in
Table I. Notice that apart from the experimental data of gra-
A. Geometrical structure and mechanical properties
phene taken from literature, all data presented here were cal-
The optimized geometric structure of octagraphene is pre- culated by ourselves using the same method. As octagons in
sented in Fig. 1(a). Carbon atoms in octagraphene form a octagraphene are larger in size than hexagons in graphene,

TABLE I. The symmetry, lattice constant (a0), bond lengths lCC, plane density q, cohesive energy (Ec), energy gap Eg between the bottom of conduction band
and the top of valence band, Young’s modulus E, breaking strength r, and Poission’s ratio  for graphene, octagraphene, graphyne, and graphdiyne,
respectively.

Structure Method Symmetry a0 (Å) ICC (Å) p (mg/m2) Ec (eV/atom) Eg (eV) E (N/m) r (N/m) 

Graphene GGA C6v 2.46 1.42 0.77 7.92 0 350 38.4,34.8 0.21,0.17
Graphene Exp.1,30–33 C6v 2.458 1.419 0.77 7.37 0 340 6 50 42 6 4 0.165
Octagraphene GGA C4v 3.45 1.48,1.35 0.68 7.39 4.03 306,168 34.4,27.3 0.13,0.47
Graphyne GGA C6v 6.88 1.22,1.42 0.59 7.26 0.48 245 23.4,19.5 0.38,0.41
Graphdiyne GGA C6v 9.45 1.23,1.43 0.47 7.14 0.51 174 16.8,13.4 0.41,0.44

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074315-3 Sheng et al. J. Appl. Phys. 112, 074315 (2012)

FIG. 3. (a) Stress-strain curves of graphene (GE),

octagraphene (OGE), graphyne (GY), and graph-
diyne (GDY) along armchair (AC) and zigzag
(ZZ) or sawtooth (ST) directions. The experimen-
tal data of graphene are taken from Ref. 30.
(b) Valence electron density of octagraphene.

octagraphene has the density (0.68 mg/m2) slightly smaller semimetal or a zero-gap semiconductor because its valence
than that of graphene (0.77 mg/m2). and conduction bands touch at K points, while graphyne and
Now let us discuss the mechanical properties of octagra- graphdiyne are semiconductors with narrow band gap of
phene. As it has a C4v symmetry, only three elastic constants 0.48 and 0.51 eV, respectively.
cij are independent. Our DFT calculations estimate that the The projected DOS of octagraphene shows that the
values of c11, c12, and c44 of octagraphene are 296, 46, and energy bands near the Fermi surface are predominantly con-
49 N/m, respectively. The Young’s modulus E of octagra- tributed by the 2pz orbital of carbon atom, forming the same
phene is obtained to be 306 and 168 N/m along the sawtooth p-bond as that in graphene. The Fermi surface of octagra-
and armchair directions (see below), respectively, in compari- phene is plotted in Fig. 4(b), which consists of a hole pocket
son to those of graphene 350 N/m, graphyne 245 N/m, and at C point and an electron pocket at M point. Since each unit
graphdiyne 174 N/m. The stress-strain curves for graphene, cell contributes four electrons with two bonding states and
octagraphene, graphyne, and graphdiyne under a uniaxial ten- two antibonding states, each point in the Brillouin zone
sion along two nonchiral directions are illustrated in Fig. 3(a). should be filled with 2  2 electrons, and the number of
The ultimate tensile strength or the breaking strength r of unoccupied states in valence band is just equal to that of
octagraphene is 34.4 and 27.3 N/m along the sawtooth and occupied states in conduction band, resulting in that the hole
armchair directions, respectively, which are quite comparable and electron pockets share the same area.
with those of graphene 38.4 N/m (zigzag direction) and
34.8 N/m (armchair direction) but larger than those of graph- C. Low-energy physics
yne (23.4 and 19.5 N/m) and graphdiyne (16.8, 13.4 N/m).
To describe the low-energy physics near the Fermi sur-
The experimental values30 of E and r for graphene are
face of octagraphene, we propose a tight-binding model
340 6 50 N/m and 42 6 4 N/m, respectively, showing that our
which contains only p electrons with nearest neighbor hop-
DFT calculations are quite reliable. The Poisson’s ratio of
pings. The Hamiltonian can be written as
octagraphene is 0.13 (sawtooth direction) and 0.47 (armchair X † X †
direction), which are comparable with 0.21 (zigzag direction) H¼t c i;r c^j;r þ h:c:Þ þ t0
ð^ ð^
c i;r c^j;r þ h:c:Þ; (1)
and 0.17 (armchair direction) of graphene. The Poisson’s ratio hi;ji;r i;j;r
of graphyne and graphdiyne can be found in Table I. From
above results, we see that octagraphene has the mechanical where c^i;r and c^†i;r are the electron annihilation and creation
properties very similar to graphene and might be the strongest operators at site i with spin r, hi; ji runs over the nearest
carbon atomic sheet after graphene till now. neighbors within the same square and t is the corresponding
hopping amplitude of electrons,  i; j  runs over the near-
B. Electronic structures est neighbors connecting different squares and t0 is the corre-
sponding hopping amplitude. In the matrix form, the
The valence electron density, electronic structures, and Hamiltonian reads
the DOS of octagraphene are obtained by means of the DFT
0 1
and TBA calculations, respectively. From Fig. 3(b), one may 0 t t0 eiky t
see that more electrons are distributed on the inter-square B t 0 t t0 eikx C
B C
bonds than on the intra-square bonds in octagraphene, which Hk ¼ B 0 iky C; (2)
@t e t 0 t A
is well consistent with its structural feature, showing an
unequal sp2 hybridizing character. The electronic structures t t0 eikx t 0
in Fig. 4(a) show that octagraphene is a semimetal, as its top
of valence band and the bottom of conduction band are where kx and ky are x and y components of momentum of p
located at C and M points in the Brillouin zone, respectively, electrons, and the lattice spacing a0 ¼ 1 is taken. The disper-
giving rise to an indirect negative band gap (4.03 eV), and sion E(k) of octagraphene within the TBA is determined by
leading to the Fermi level passes through both the conduc-
2
tion and valence bands. Thus, in contrast to graphene, the EðkÞ4  2ðt0 þ 2t2 ÞEðkÞ2 þ 4t0 t2 ðcos kx þ cos ky ÞEðkÞ
charge carriers in octagraphene have both holes and elec- 2 2
trons around the Fermi level. Note that graphene is also a þ t0 ½t0  4t2 ðcos kx þ cos ky Þ ¼ 0: (3)

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074315-4 Sheng et al. J. Appl. Phys. 112, 074315 (2012)

FIG. 4. (a) Electronic band structures and den-

sity of states (DOS) of octagraphene calculated
by the density functional theory (DFT) and the
tight-binding approximation (TBA) methods.
(b) Fermi surface of octagraphene, where the
hole packet (red) is at C point, and the electron
pocket (blue) is at M point. (c) Energy bands of
octagraphene nanotubes (3,3), (5,5), (12,12),
(5,0), (8,0), and (16,0).

The TBA results are in good agreement with those (OCNT) by C ~h ¼ n~a 1 þ m~ a 2  ðn; mÞ, where n and m are
obtained by the DFT calculations [Fig. 4(a)], implying that the integers with 0 jmj n because of the C4v symmetry. We
low-energy properties of p electrons in octagraphene can be call (n, 0) the sawtooth OCNT (m ¼ 0, c ¼ 0 ) and (n, n) the
well described by the TBA Hamiltonian, where the fittings give armchair OCNT (m ¼ n, h ¼ 45 ), where the chiral angle is
t ¼ – 2.5 eV and t0 ¼ – 2.9 eV. For graphene, t ¼ –2.7 eV.34 pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
defined as cos h ¼ n= n2 þ m2 . The tube diameter is given
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
by dt ¼ jC ~h j=p ¼ a0 n2 þ m2 =p. The geometric structures
D. Fabricating suggestions of sawtooth OCNT (10,0) and armchair OCNT (8,8) are pre-
To obtain the structure of octagraphene experimentally, sented in Fig. 1(b) as examples, whose structural stabilities
we suggest that one may make the line defects periodically were verified by the DFT calculations. The energy bands of
in graphene and then connect properly the broken bonds of OCNT (3,3), (5,5), (12,12), (5,0), (8,0), and (16,0) are given
carbon atoms, as demonstrated in Fig. 5. In addition, it may in Fig. 4(c), which show that regardless of the curvature
be possible to synthesize it through the acetylene scaffolding effect, the single-walled OCNTs, either sawtooth or arm-
ways.10,18 chair, are all metallic.
In addition, by wrapping octagraphene and using penta-
gons, hexagons, or heptagons as caps, many structurally sta-
IV. OCTAGRAPHENE NANOTUBES AND FULLERENES ble unconventional carbon fullerenes can be built. The
By rolling octagraphene, the novel single-walled carbon optimized examples like C36, C48, C80, and C96 are shown in
nanotubes can also be obtained. For this purpose, let us Fig. 1(c). These results show that octagraphene is indeed a
~h of octagraphene carbon nanotube
define the chiral vector C versatile 2D crystalline allotrope of carbon after graphene.

V. BAND ENGINEERING AND HYDROGEN STORAGE

A. Boron nitrogen pair doping
Similar to graphene and carbon nanotubes,35,36 the semi-
metallic octagraphene may be applicable in the band engi-
neering via the chemical doping. In fact, our calculation
reveals that a band gap opens if the octagraphene is substitu-
FIG. 5. A schematic demonstration how to utilize the line defects in gra- tionally doped with boron and nitrogen (B-N) pairs, as
phene to obtain octagraphene. shown in Fig. 6, where 11 structures for different doping

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074315-5 Sheng et al. J. Appl. Phys. 112, 074315 (2012)

supercell is replaced by eight B-N pairs; in the eighth one, a

cross is replaced by 14 B-N pairs; the tenth one is the dual
structure of the eighth; and the eleventh is the dual structure
of the fifth. The band gap varies significantly for different
doping configurations, as shown in Fig. 6(b). It is seen that
the boron nitrogen pair doped octagraphene can open a gap
from 0.009 eV (structure 2) to 1.866 eV (structure 11), which
can gain some insights for nanoelectronics. It is noting that
the band gaps of most of the structures considered here are
around 0.2 eV, even when the doping concentration is as
large as 50.82% (structure 9), which is quite different from
the doped graphene.37 Considering that the GGA usually
underestimates the band gap, the present doping study gives
useful information for the band engineering in octagraphene.

B. Hydrogen storage
Next, let us consider the possibility of hydrogen storage
in octagraphene. In general, there are two ways to realize
this purpose. One is that hydrogen atoms can be absorbed on
carbons via the chemical bond to form a new hydrocarbon
sheet, similar to graphane;14 the other is that the hydrogen
molecules can be adsorbed physically on some metal atoms
(e.g., Ti, Ca, Al, etc.) that are deposited on the sheet of octa-
graphene. In the former case, the hydrogen storage capacity
of octagraphene can reach 7.7 wt. % as graphane does.14 In
the latter case, the hydrogen capacity depends on the adsorp-
tion configuration of metal atoms. There are five possible
adsorption positions for metal atoms (see Fig. 7), including
one top site on C atoms (T), two bridge sites on top of intra-
square (B) and inter-square (B0 ) C-C bond, respectively, and
two hollow sites on top of square (H) and octagon (H0 ),
respectively. To analyze the stability of these five adsorption
configurations, we calculate the cohesive energy EbM with
M the adsorbed metal atom by

EbM ¼ ½Eocta þ nEM  EMocta =n; (4)

FIG. 6. (a) Schematic structures of boron nitrogen pairs substitutionally

doped octagraphene with different doping configurations, where carbon,
boron, and nitrogen atoms are colored in blue, red, and green, respectively.
(b) The corresponding band gaps (Eg) for different structures of (a), where
the doping concentration is from small to large in sequence.

configurations and a pure B-N octa-square structure are con-

sidered. All these doped structures are energetically favor-
able. In Fig. 6(a), the structures of number 1-11 are those of
octagraphene of 4  4 supercell with substituting carbon
(blue ball) by boron (red ball) and nitrogen (green ball) atom
pairs, and the structure of number 12 is the pure B-N octa-
gon-square structure of 3  3 supercell. In the first structure,
two carbon neighbors are replaced by one B-N pair; in the
second (third) structure, a square (octagon) is substituted by
FIG. 7. There are five possible adsorption sites of metal atoms on octagra-
two (four) B-N pairs; in the fourth (sixth, seventh or ninth) phene, including one top site on C atoms (T), two bridge sites on top of
one, a nanoribbon in octagraphene is substituted by four intra-square (B) and inter-square (B0 ) C-C bond, respectively, and two hol-
(eight, twelve or sixteen) B-N pairs; in the fifth one, a 2  2 low sites on top of square (H) and octagon (H0 ), respectively.

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074315-6 Sheng et al. J. Appl. Phys. 112, 074315 (2012)

hole pocket and one electron pocket. In order to describe the

low-energy physics of octagraphene, we also suggest a tight
binding model of p electrons which is uncovered to agree well
with DFT calculations and is quite helpful for further explor-
ing the properties of octagraphene in a magnetic field or emer-
gent quantum phenomena such as quantum Hall effect, Kondo
effect, and so on in octagraphene. The intriguing mechanical
properties of octagraphene are also obtained, which are
observed close to those of graphene. Similar to graphene, we
find that octagraphene can also be rolled seamlessly to form
stable carbon nanotubes and unconventional fullerenes. By
substitutionally doping boron nitrogen pairs, we disclose that
the semimetallic octagraphene can be turned into a semicon-
ductor with a band gap, the property will be useful for possi-
ble applications in nanoelectronics. This new carbon allotrope
has also the possibility for hydrogen storage. Our calculation
shows that for the 2D octagraphene sheet, the hydrogen stor-
FIG. 8. The configuration of four hydrogen molecules adsorbed on each Ti age capacity could reach 7.76% via Ti-adsorption that is close
atom at H1 site. (a)-(d) reveal the single-side hydrogen storage configura-
tions with one, two, three, and four hydrogen molecules adsorbed on each Ti
to that of graphene. Finally, we would like to mention that
atom, respectively; (e)-(h) show the double-side hydrogen storage configura- one might obtain this new kind of carbon atomic sheet via
tions with one, two, three, and four H2 adsorbed on each Ti atom, respec- making line defects in graphene or through the acetylene scaf-
tively; where C, Ti and H atoms are colored in dark blue, bluish green, and folding ways.
brick red, respectively.

where Eocta, EM and EM–octa are the total energies of pure ACKNOWLEDGMENTS
octagraphene, M atom, and octagraphene with adsorbed We are grateful to Dr. Eric Germaneau for useful discus-
metal M, respectively. For Ti doping (M ¼ Ti), H site is the sions. All calculations were completed in the Shanghai
most stable position with cohesive energy of 2.71 eV per Ti Supercomputer Center, China. This work was supported by
atom. the NSFC (Grants Nos. 90922033, 10934008, 10974253,
Figs. 8(a)–8(d) present single-side hydrogen storage 10904081, and 11004239), the MOST of China (Grant No.
configurations with one, two, three, and four hydrogen mole- 2012CB932900), and the CAS.
cules adsorbed on each Ti atom. The average adsorption
energy per H2 is 0.207 eV, 0.361 eV, 0.336 eV, and 0.325 eV,
respectively. Figs. 8(e)–8(h) give double-side hydrogen stor- 1
K. S. Novoselov, A. K. Geim, S. V. Morozov, D. Jiang, Y. Zhang, S. V.
age configurations with one, two, three, and four H2 Dubonos, I. V. Grigorieva, and A. A. Firsov, Science 306, 666 (2004).
2
A. Geim, Science 324, 1530 (2009).
adsorbed on each Ti atom. The average adsorption energy 3
A. H. Castro Neto, F. Guinea, N. M. R. Peres, K. S. Novoselov, and A. K.
per H2 is 0.235 eV, 0.355 eV, 0.336 eV, and 0.325 eV, Geim, Rev. Mod. Phys. 81, 109 (2009).
4
respectively. In this case, the hydrogen storage capacity N. M. R. Peres, Rev. Mod. Phys. 82, 2673 (2010).
5
could reach 7.76 wt. % for Ti [as shown in Fig. 8(h)], which V. H. Crespi, L. X. Benedict, M. L. Cohen, and S. G. Louie, Phys. Rev. B
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