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Yttrium-dispersed B80 fullerenes: Promising materials for hydrogen storage

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 March 2015
EPL, 109 (2015) 56004 www.epljournal.org
doi: 10.1209/0295-5075/109/56004

Yttrium-dispersed B80 fullerenes: Promising materials

for hydrogen storage
W. W. Wu, Z. Y. Tian and S. L. Dong(a)

Department of Physics, Ocean University of China - Qingdao 266100, China

received 30 August 2014; accepted in final form 26 February 2015

published online 18 March 2015
PACS 68.43.-h – Chemisorption/physisorption: adsorbates on surfaces
PACS 61.46.-w – Structure of nanoscale materials
PACS 73.22.-f – Electronic structure of nanoscale materials and related systems

Abstract – We report a first-principles study, which predicts that a single yttrium atom dec-
orated on B80 fullerenes can maximally hold up six H2 molecules with an average binding en-
ergy of −0.55 eV/H2 . The analysis with 12 Y atoms placed at the pentagons of B80 fullerenes
showed no clustering effect, and the resulting B80 Y12 complex can remarkably bind up to 71 H2
molecules, yielding a gravimetric storage capacity of 6.85 wt%. The interaction between hydrogen
molecules and B80 Y12 complex is attributed to the Dewar-Kubas mechanism involving the empty
Y-d orbitals, H2 -σ orbitals and H2 -σ ∗ antibonding orbitals. Our work suggests a new route to bet-
ter hydrogen storage material and advances our fundamental understanding of reversible hydrogen
adsorption in nanostructures.

Copyright 
c EPLA, 2015

Introduction. – Hydrogen has widely been considered For instance, Yildirim and co-workers have found that
as an alternative energy resource due to its non-pollution, a single Ti atom coated on SWNT can bind up to four
abundant sources and renewable nature [1,2]. However, hydrogen molecules with three molecular and one disso-
traditional methods of hydrogen storage involving com- ciative adsorption [19]. This result is a fundamental step
pression, liquefaction and adsorption in metal alloys do towards novel materials applied on hydrogen storage. Sim-
not satisfy the practical requirement, and even safety ilarly, alkali- and alkaline-earth metals like Li, Na and Ca
problems have limited its further development [3]. Thus, supported on nanomaterials are found to have promoted
the substantial difficulty is finding new materials with high the hydrogen uptake [20,21]. Unfortunately, such metal
gravimetric and volumetric densities and reversibility in atoms tend to form clusters on the surface of nanomateri-
terms of hydrogen storage under ambient conditions [4,5]. als due to their huge cohesive energies and relatively low
A review of the previous literature shows that nanoma- binding energies to the host materials [22–26].
terials can serve as an attractive candidate for hydrogen Recently, Szwacki et al. have predicted an unusually
storage applications [6–11]. Dillon et al. have pioneered stable boron cage with 80 boron atoms, which preserves
the idea that hydrogen molecules can condense to single- the icosahedral symmetry (Ih ). Although there are no
walled nanotubes (SWNTs) with a high gravimetric den- more than 20 atoms of the boron clusters identified exper-
sity of ∼5–10 wt% [12]. However, the subsequent studies imentally, analyses convincingly present the B80 fullerenes
have argued the point that the hydrogen molecules are as a promising cage which would be the second example
bound weakly to the host nanomaterials via the simple after C60 [27]. The basic structure of B80 is similar to
van der Waals interaction, thus they can desorb easily at that of the typical C60 fullerenes except for an additional
low temperatures [13]. In light of this, recent studies have boron atom at the center of each hexagon. Later, the B80
intensively explored carbon nanotubes and fullerenes deco- fullerenes yielding a puckered cage were found to be more
rated with transition metals for desired storage character- stable in the reduced tetrahedral (Th ) symmetry [28,29].
istics where the hydrogen molecules get adsorbed around In this view, B80 fullerenes decorated with metal atoms
the dopant through the Dewar-Kubas interaction which have been reported in recent literature for increasing the
is more suitable for room temperature storage [14–18]. hydrogen storage capacity [30–33]. Li et al. proposed
Ca-dispersed B80 as a promising hydrogen storage mate-
(a) E-mail: [email protected] (corresponding author) rials based on the GGA method. Furthermore, Ca atoms

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W. W. Wu et al.

(a)

Fig. 1: (Colour on-line) (a) Optimized structure of the B80 Y

complex, where the Y atom is adsorbed at pentagonal site.
(b) Full coverage case with twelve Y atoms located at all avail-
able pentagonal sites.

binding to B80 fullerenes are found to be enhanced consid-

erably, avoiding the thorny clustering problem [34]. Their
results, which are significant for safe and efficient hydro-
(b)
gen storage, inspired us to consider the metal-coated B80
as the substrate material for hydrogen storage.
Fig. 2: (Colour on-line) (a) The partial density of states
In this paper, we find that yttrium-dispersed B80 (PDOS) for B80 Y complex, where the red and blue lines rep-
(B80 Y12 ) can bind up to 71 hydrogen molecules with a resent the B-p and Y-d orbitals. The vertical straight line de-
gravimetric density of 6.85 wt%, exceeding the Depart- notes the Fermi level. (b) The charge density difference of
ment of Energy (DOE) target (6.5 wt%). Notably, Y B80 Y complex. The blue and pink regions represent electron
atoms can be prevented from clustering in a macroscopic accumulation and depletion, respectively.
sample, which is critical for the storage of a large amount
of hydrogen. In addition, we present the theoretical ap- under the Y-dopant is slightly elongated from 1.741 Å to
proach and the details of calculated results on the hy- 1.772 Å.
drogen adsorption obtained from an accurate quantum To illustrate the binding mechanism between the Y
chemical calculation. atom and B80 , we have carried out the partial density
of states (PDOS) of the B80 Y complex, as displayed in
Computational methods. – Our calculations were fig. 2(a). The isolated Y atom has available empty d or-
performed within the density functional theory (DFT) bitals, leading to a high chemical activity as it approaches
method by using the ab initio code (SIESTA) [35]. B80 fullerenes. After loading on the B80 surface, the Y-d
The generalized gradient approximation (GGA) with the orbitals near the Fermi level are split into several degen-
Perdew-Burke-Ernzerhof (PBE) functional was employed erated states under the strong ligand field generated by
for the exchange correlation of electrons [36]. The valence the B80 fullerenes. Meanwhile, the Y-d orbitals are par-
electrons were described using a double-ζ basis set of lo- tially occupied and this is consistent with the Mulliken
calized numerical atomic orbitals, including polarization population analysis. We find that the Y atom carries
functions (DZP). The optimized structures were carried 0.17e positive charge, suggesting that B80 fullerenes back
out in a 20 × 20 × 20 Å supercell to eliminate possible in- donates part of its received electrons to the Y-d orbitals,
teractions between adjacent images. The Gamma point resulting in a strong hybridization between the B-π and
was used to represent the Brillouin zone and a mesh cut- Y-d orbitals and partial occupancy of Y-d orbitals. This
off energy was set to 200 Ry [37]. The structure was fully hybridization leads to a strong interaction between the Y
relaxed until the maximum atomic force was less than atom and B80 , which contributes to holding the Y atom
0.03 eV/Å. stably on the fullerenes. Furthermore, loss of π bond-
Results and discussion. – Our results indicate that ing orbitals between neighboring B atoms can be observed
the Y atom prefers to bind firmly above the center of the upon metal adsorption, which is responsible for the elonga-
pentagon (P site), as shown in fig. 1(a). The binding en- tion of the B-B bond. This is also evident from the charge
ergy of the Y atom on B80 is calculated from the expression density differences (Δρ) of B80 Y, as shown in fig. 2(b).
It is measured by subtracting charge densities of the Y
Eb (Y) = E(B80 Y) − E(B80 ) − E(Y), atom and bare fullerenes from that of the B80 Y complex.
It is seen that the charge depletes from the Y-dopant and
where E(B80 Y), E(B80 ), and E(Y) are the total energy of accumulates in the region between the adsorbed Y atom
B80 Y complex, the bare fullerenes and the free Y atom, and B80 . Clearly, the charge transfer leaves the Y atom
respectively. The binding energy of the Y atom is calcu- in cationic form, providing a possible adsorption of hy-
lated to be −4.67 eV. The average distance of Y atom to drogen molecules by the metal cation via the polarization
the nearest B atoms is 2.541 Å while the B-B bond length mechanism.

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 Yttrium-dispersed B80 fullerenes: Promising materials for hydrogen storage

Table 1: Average binding energy of hydrogen molecule (Eb ), calculated bond lengths of Y-B, Y-H and H-H, overlap populations
between Y atom and B80 fullerenes, and Mulliken charges.

System Eb (eV) dY -B (Å) dY -H (Å) dH-H (Å) PY -B Mulliken charge Y/H2 (e)
B80 YH2 −0.34 2.548 2.369 0.803 0.177 0.189/− 0.006
B80 Y(H2 )2 −0.56 2.567 2.305 0.814 0.164 0.307/− 0.044
2.206 0.853 −0.121
B80 Y(H2 )3 −0.59 2.590 2.303 0.810 0.151 0.409/− 0.046
2.237 0.839 −0.114
2.230 0.842 −0.118
B80 Y(H2 )4 −0.58 2.603 2.309 0.807 0.147 0.485/− 0.061
2.242 0.836 −0.118
2.245 0.828 −0.111
2.295 0.806 −0.063
B80 Y(H2 )5 −0.57 2.613 2.316 0.801 0.138 0.640/− 0.061
2.260 0.823 −0.114
2.253 0.826 −0.138
2.284 0.810 −0.083
2.298 0.816 −0.116
B80 Y(H2 )6 −0.55 2.678 2.282 0.804 0.119 0.997/− 0.087
2.281 0.825 −0.144
2.268 0.828 −0.155
2.293 0.822 −0.131
2.288 0.821 −0.133
2.273 0.828 −0.151

In order to check whether Y atoms form clusters on

the host substrate, we place 12 Y atoms separately at the
centers of 12 pentagons, resulting in a highly geometric
symmetry structure as shown in fig. 1(b). The average
binding energy per Y atom in B80 Y12 is −4.62 eV, compa-
rable to that of −4.67 eV in B80 Y. Our structural relax-
ation with multiple Y atoms shows that the Y-Y distances
become 6.414 Å, which is much larger than the Y-Y bond
length (3.55 Å) in bulk phase, excluding the possibility
of Y clustering on B80 . Earlier study carried out by
Chakraborty et al. also showed a similar conclusion, i.e.,
that the Y adatoms on SWNTs are not clustering even at
high temperature due to the presence of a 0.6 eV energy
barrier [17]. To further verify the stability of B80 Y12 com-
plex at high temperature, we perform molecular dynamics
(MD) simulations by using Nose algorithm with 1 fs time
steps [38]. We have totally carried out 5 ps MD simula- Fig. 3: (Colour on-line) Panels (a)–(f) show the optimized
tions with temperatures ranging from 300 K to 800 K, and structures of B80 Y(H2 )n when n increases from 1 to 6.
found that the structure is still stable without any cluster
formation except for small fluctuations in bond length. where E(. . .) is the total energy of corresponding struc-
Now we explore the H2 storage capacity of the B80 Y ture, and other geometrical parameters are summarized
complex by calculating the interaction with a different in table 1.
number of H2 molecules. In the optimized configuration Upon attaching to the Y atom, the first H2 molecule
described in fig. 3, a single Y atom on B80 can adsorb up is weakly adsorbed with a binding energy of −0.34 eV.
to six H2 molecules with a relatively high symmetry. The From Mulliken charge analysis, we note that the first H2
average binding energy per H2 is calculated by molecule gains only 0.006e charge, indicating that the
charge polarization mechanism is crucial for this H2 ph-
Eb (H2 ) = [E(B80 Y + nH2 ) − E(B80 Y) − nE(H2 )]/n, ysisorption, rather than the charge transfer mechanism.

56004-p3
W. W. Wu et al.

Therefore, the presence of H2 molecule has slight effects

on the interaction between the Y atom and B80 , and the
Y-B bond is calculated to be 2.548 Å. Meanwhile, the
H2 molecule is located on the top of the Y atom with a
relatively large Y-H bond (2.369 Å), implying a weak ph-
ysisorption. As additional H2 molecule approaches B80 Y
complex, there are amounts of charge transfer from the
Y-dopant to H2 molecule, indicating that the charge trans-
fer is responsible for the subsequent hydrogen adsorp-
tion. We find that the second H2 molecule gets adsorbed
molecularly with a significant increase in binding energy
(−0.56 eV), accompanied by a decreased Y-H bond length
of 2.206 Å. Actually, this is a chemisorption process which
can be confirmed from the Mulliken population analysis
that about 0.121e electrons are transferred from the Y
atom to H2 molecule. These electrons are forced to oc-
cupy the antibonding orbitals of the H2 molecule, leading
to an elongated H-H bond of 0.853 Å. Remarkably, as the
number of H2 molecules increases, we note that a single Y
atom can adsorb up to six H2 molecules without breaking
the Y-B bonds and all attachments are molecular in com-
parison to Ti-decorated C60 [39]. The binding energies
for successive H2 adsorption are −0.59, −0.58, −0.57 and (a)
−0.55 eV, respectively. It is clear that the adsorption of
H2 molecules further weakens the interaction between the
Y atom and B80 , and the Y-B bond length stretches to
2.678 Å. The result reveals that the weakening of the Y-B
bonds would lead to the transfer of charge from Y-B bonds
to Y-H bonds, resulting in an enhanced hydrogen storage
capacity. This is also well manifested by the overlap popu-
lation analysis that the binding strength of the Y-B bond
is a decreasing function of the coordination number. The
attempts to introduce more than six H2 molecules to the
Y atom have failed. As shown in fig. 3(f), the H2 molecule (b)
paralleled to the plane of B80 Y(H2 )5 is physically adsorbed
with the weakest bonding in the system, whereas the side Fig. 4: (Colour on-line) (a) The PDOS for the B80 Y(H2 )n
system (n = 1–6). The green, red and blue lines represent the
H2 molecules are chemisorbed, exhibiting a regular pen-
H-s, B-p and Y-d orbitals, respectively. The vertical straight
tagon configuration.
line denotes the Fermi level. (b) Charge density differences
The above discussion is substantiated by the PDOS of 3
with an isovalue of 0.0035 e/Å for the system of B80 Y(H2 )6 .
the B80 Y complex with different number of H2 molecules.
The binding states as shown in fig. 4(a) have a major
3
contribution from the Y-d orbitals, together with the B-p upon H2 adsorption. The isosurface (Δρ = ±0.0035 e/Å )
orbitals and H-s orbitals. We found that the Y-d orbitals of charge density differences is shown in fig. 4(b), with
around the Fermi level is decreasing with the increase of the blue and pink representing the electron accumulation
H2 molecules. As in the case of B80 Y(H2 )6 , the H2 -σ or- and depletion regions, respectively. Due to further charge
bitals spread out with several main peaks about −12 eV transfer from the Y atom to H2 molecule, the Y site be-
below the Fermi level and weakly hybridize with the Y-d comes more positively charged, and the electrons accumu-
orbitals. Similarly, the overlap of states at −2 eV is the late in the middle of the H2 molecules while the electrons
simultaneous hybridization of the H2 -σ ∗ antibonding or- depletion occurs on both ends. Clearly, the H2 molecules
bitals with Y-d orbitals. Since the mechanism of the in- are polarized. Thus, we can conclude that the efficient
teraction seems to be very similar to the Dewar-Kubas hydrogen storage of B80 Y mainly comes from both the
interaction [40], in which the H2 molecules donate their Dewar-Kubas interaction and the polarization effect.
σ electrons to the vacant metal-d orbitals, while the filled If the Y atoms are doped at all the available 12 pentag-
d orbitals back-donate electrons to the H2 -σ ∗ antibonding onal sites, it can be expected that 72 H2 molecules can be
orbitals. Finally, the peak around −2 eV is related to the adsorbed by the B80 Y12 . The optimized configuration of
hybridization among Y-d orbitals and B-p orbitals, demon- B80 Y12 (H2 )72 , as shown in fig. 5, indicates that at each
strating that the formation of Y-B bond is still stable Y site, four H2 molecules bind to the side of the Y atom

56004-p4
 Yttrium-dispersed B80 fullerenes: Promising materials for hydrogen storage

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