J Nanopart Res (2012) 14:1263
DOI 10.1007/s11051-012-1263-0
RESEARCH PAPER
Adsorption and dissociation of molecular hydrogen
on the edges of graphene nanoribbons
Cecilia Bores • Iván Cabria • Julio A. Alonso
Marı́a J. López
Received: 20 January 2012 / Accepted: 22 October 2012 / Published online: 9 November 2012
Ó Springer Science+Business Media Dordrecht 2012
Abstract The dissociation and adsorption of molec-
ular hydrogen on the edges of graphene nanoribbons of
widths of 1.14 and 1.36 nm, is investigated within the
density functional formalism. Here, graphene nano-
ribbons are used as models for the pore walls of some
nanoporous carbons (carbide-derived carbons among
others) which have been shown to be formed by one-
atom thick graphene layers interconnected among
them and exhibiting exposed edges (López et al. in J
Chem Phys 135:104706, 2011). The aim of this study is
to shed some light on the contribution of the edges of
the pore walls to the hydrogen storage capacity of
nanoporous carbons. Nanoribbons with zigzag and
armchair edge terminations have been considered.
Molecular hydrogen dissociates and adsorbs atomi-
cally at the nanoribbon edges with no or small
activation barrier. The adsorption energies per hydro-
gen molecule are quite large, 2.5 and 5.7 eV for
armchair and zigzag edges, respectively. This indicates
that the graphene edges are very reactive and will be
saturated with hydrogen whenever available. How-
ever, under mild conditions of pressure and tempera-
ture hydrogen cannot be desorbed from the edges and,
This article is part of the topical collection on nanomaterials in
energy, health and environment
C. Bores  I. Cabria  J. A. Alonso  M. J. López (&)
Departamento de Fı́sica Teórica, Universidad de
Valladolid, 47011 Valladolid, Spain
e-mail: maria.lopez@fta.uva.es
•
therefore, the edges do not contribute to the reversible
storage capacity of the material. The magnetic prop-
erties of saturated and unsaturated ribbons are also
discussed.
Keywords Graphene  Hydrogen dissociation 
Ribbons  Hydrogen storage  Theory,
modeling, and simulation
Introduction
Hydrogen is a promising alternative to fossil fuels for
automotive applications. However, the on-board stor-
age of hydrogen remains as a challenging technolog-
ical problem. Hydrogen storage on nanoporous carbon
materials stands out as one of the best options. The
storage capacity of carbide-derived carbons (CDC)
(Gogotsi et al. 2005) and activated carbons (AC)
(Linares-Solano et al. 2008) is about 6 wt% of hydro-
gen at low temperatures (77 K). However, at room
temperature these materials exhibit a much smaller
capacity of about 1 wt% of hydrogen which is far to
comply with the technological requirements of
5.5 wt% hydrogen (DOE 2009). Hydrogen storage on
nanoporous carbons, is driven by the adsorption
(physisorption) of molecular hydrogen on the pore
walls of the material. Many studies have investigated
the adsorption of molecular hydrogen on graphitic
walls (Arellano et al. 2000; Alonso et al. 2004;
Pradhan et al. 2002; Froudakis 2002). The main result
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Page 2 of 9
is that the adsorption energy is quite small, about
100 meV, what explains the small hydrogen storage
capacity of nanoporous carbons at room temperature
(Gogotsi et al. 2005; Linares-Solano et al. 2008).
Moreover, it has been shown (Arellano et al. 2002)
that the dissociative adsorption (chemisorption) of
hydrogen on graphitic surfaces is an endothermic
process with high (higher than 3 eV) activation
barriers and, therefore, this process does not contribute
to the storage capacity of nanoporous carbons. In
contrast, some metal surfaces are able to catalyze the
dissociation of molecular hydrogen (Hammer and
Nørskov 1995). Hydrogen dissociation has activation
barriers in Al and Cu surfaces. However, there is no
activation for the dissociation of H2 on Pt(111) or on Pt
at the Cu3Pt surface. The dissociation barriers are not
determined exclusively by the density of states, DOS,
of the d-band at the Fermi level and the number of
empty d states above the Fermi energy. The dissoci-
ation barriers can be understood in terms of the
hybridization energy between the bonding and anti-
bonding adsorbate states and the metal d bands (when
present). The optimal size and shape of the pores for
hydrogen storage in nanoporous carbon materials,
have been also investigated (Cabria et al. 2007, 2011).
Recently, some of the authors have unraveled
(López et al. 2011) the atomistic and pore structure of
some nanoporous carbons (CDCs and similar porous
carbons). The pore walls are one-atom thick graphene
layers interconnected among them and exhibiting
exposed graphene edges. The role played by the
graphene edges of the pore walls on the adsorption of
hydrogen on nanoporous carbons has not been inves-
tigated so far. Our aim is to get some insight on the
contribution of the edges to the hydrogen storage
capacity of nanoporous carbons. As models for the
exposed edges of the pore walls, we have considered
graphene nanoribbons with armchair and zigzag
terminations. Using the density functional formalism
(DFT), we have studied the possible adsorption and
dissociation of molecular hydrogen on the ribbon
edges. Our calculations show that the molecular
hydrogen dissociates without or with small activation
barriers on the proximity of both, zigzag and armchair
edges, and binds atomically on the edges with energies
of 2.5 and 5.7 eV/molecule in the armchair and zigzag
edges, respectively. Clearly, the unsaturated carbon
edges of the nanoribbons are very active chemically
and therefore, adsorb hydrogen readily, whenever
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J Nanopart Res (2012) 14:1263
available. However, this adsorbed hydrogen would not
contribute to the reversible storage capacity of nano-
porous carbons, since it cannot be released at room
temperature.
Tight binding (TB) calculations have revealed the
existence of electronic states localized on the zigzag
edges of graphene nanoribbons (Kobayashi 1993;
Fujita et al. 1996; Nakada et al. 1996). These edge
states have been confirmed through density functional
calculations for both, bare (Barone et al. 2006; Okada
2008) and saturated edges (Son et al. 2006a, b), and
have been demonstrated experimentally in STM
measurements (Kobayashi et al. 2005; Tao et al.
2011). The edge states at each edge have different
spin polarizations giving rise to an antiferromagnetic
ordering between the edges and a total spin of the
ribbon S=0. Armchair edges (saturated with hydro-
gen), however, do not exhibit such edge states.
Moreover, it has been shown that the edges of zigzag
carbon nanotubes of finite length do also exhibit spin-
polarized edge states (Mañanes et al. 2008). Interest-
ingly, it has been shown in the literature that carbon/
graphene-based materials may exhibit magnetic
moments (Shibayama et al. 2000; Rode et al. 2004).
The non-compensated spins giving rise to a net
magnetic moment originate from the graphene edge
states. Here, we compare the magnetic behavior of
zigzag and armchair nanoribbons with exposed edges
and with hydrogen-saturated edges. We also show a
novel effect on the ribbons: the adsorption of hydrogen
on only one edge of zigzag nanoribbons induces a
magnetic moment on the ribbon of 2 lB per adsorbed
molecule. This suggests a possible pathway to tailor
the magnetic moment in carbon materials. The struc-
ture of the paper is as follows: in ‘‘Theoretical model’’
section, we present the methodology and computa-
tional details. In ‘‘Results’’ section gives the results on
the adsorption of hydrogen on zigzag and armchair
nanoribbons and on the magnetic properties of the
ribbons. Finally, in ‘‘Summary’’ section, we present
the summary and conclusions.
Theoretical model
As models for the graphitic walls of nanoporous
carbon materials, we have considered graphene nano-
ribbons. The ribbons are obtained by cutting a
graphene layer along two parallel lines. Ribbons with
J Nanopart Res (2012) 14:1263
Fig. 1 Structure of a a (a)
zigzag terminated ribbon
(infinite length in the
X direction) consisting on
six zigzag chains (Nz labels
the chains) and b an
armchair-terminated ribbon
(infinite length in the
Y direction) consisting on
six armchair chains (Na
labels the chains). The
ribbon widths are 1.14 and
1.36 nm, respectively. The
relaxed C–C bond lengths
(calculated using the PW91
functional) are indicated in
the figure in units of 100 pm
zigzag or armchair edges are produced when the
cutting lines form an angle of 0° or 30°, respectively,
with a unit vector of the graphene lattice. We consider
ribbons formed by six zigzag or six armchair chains as
shown in Fig. 1. These ribbons have similar widths of
1.14 and 1.36 nm, respectively.
We have used the DFT to investigate the electronic
and magnetic properties of graphene nanoribbons and
the adsorption of molecular hydrogen on the ribbon
edges. The DFT calculations have been performed with
the DACAPO code (DACAPO 2009). The code
implements the supercell methodology. Supercells
containing 36 and 48 carbon atoms have been used for
the zigzag and the armchair nanoribbons, respectively
(as shown in Fig. 1). The supercell dimensions in the
nonperiodic directions of the ribbons are taken large
enough (3.1 nm in the Y direction for zigzag ribbons,
3.3 nm in the X direction for the armchair ribbons and
1.4 nm in the Z direction) to avoid interactions between
the images of the ribbon in different supercells.
Vanderbilt ultrasoft pseudopotentials (Vanderbilt
1990) are used and a basis set of plane waves. The
energy cutoff is set to 350–400 eV for good conver-
gence. Since the supercells used in the calculations are
quite large, a single k-point (the C-point) in the
reciprocal lattice is sufficient to guarantee conver-
gence in the cohesive energies within 10 meV.
However, to calculate the electronic density of states,
DOS, and the band gaps we have considered 16 or 32
k-points in the first Brillouin zone following the
Monkhorst–Pack scheme (Monkhorst and Pack 1976),
plus three additional k points: the center and the edge
of the first Brillouin zone, and the point at 1/2 (2/3)
Page 3 of 9
(b)
distance from the center, for the armchair (zigzag)
ribbons. The GGA-PW91 (Perdew and Wang 1992)
exchange–correlation functional is employed. Calcu-
lations using the local density approximation (LDA) to
the exchange–correlation potential as parametrized by
Vosko–Wilk–Nusair (VWN) (Vosko et al. 1980) have
also been performed. These two exchange–correlation
functionals do not include dispersion forces. However,
the long range interaction between a hydrogen mol-
ecule (a closed shell system) and graphene is mainly
due to dispersion forces. For this reason, we have
added an empirical correction (EvdW) (Wu and Yang
2002) to the PW91 energies, to include the dispersion
(Van der Waals type) interactions between the hydro-
gen molecules and the graphene nanoribbons. We use
the so called C6 correction term (Wu and Yang 2002)
which has the form
C6
EvdW ¼ fd ðRÞ ; ð1Þ
R6
where R is the distance between each pair of atoms, the
coefficient C6 gives the asymptotic form of the Van
der Waals attraction and fd is a Fermi type damping
function
1
fd ðRÞ ¼    ð2Þ
1 þ exp b RRm  1
which is one at large values of the interatomic
distances and zero at small values. The values of the
parameters, adjusted to represent the H–C interaction,
are C6 = 3.139 9 106 eV/nm6, b = 23, and Rm =
0.16 nm.
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Page 4 of 9
Results
We have investigated graphene nanoribbons termi-
nated in zigzag and armchair edges. The structure of
the ribbons has been fully relaxed. Relaxation does not
change the zigzag or armchair character of the edge
termination of the ribbons. The relaxed structural
parameters of the ribbons are given in Fig. 1. The C–C
bond lengths at the edges experience a substantial
contraction of about 13 % with respect to the infinite
graphene layer for the armchair edges, whereas for
zigzag edges only a small contraction of about a 3 %
in the C–C bond lengths is produced. These results are
in agreement with previous LDA calculations (Okada
2008). Other possible edge reconstructions (Koskinen
et al. 2008) have not been considered here since recent
experiments (Kobayashi et al. 2005) show that edge
terminations upon annealing are only the zigzag and
armchair terminations.
Clearly, the ribbons are metastable carbon struc-
tures. The ribbon energy above the energy of the
perfect graphene layer, i.e., the ribbon formation
energy, Eformation, per unit length of ribbon is given by
Eformation ¼ ðEðribbonÞ  nEðgrapheneÞÞ=L; ð3Þ
where E(ribbon) is the energy of a ribbon supercell of
length L that contains n carbon atoms and E(graphene)
is the energy of the perfect graphene layer per carbon
atom. Since a ribbon has two edges, the formation
energy of one edge, Eedge, is half the formation energy
of the ribbon. Notice that with this definition, the
formation energy of a given edge depends on the width
of the ribbon used to compute it. The formation
energies of the zigzag and armchair edges are 11.9 and
10.1 eV/nm, respectively, as calculated from the
ribbons containing six zigzag or six armchair chains.
Therefore, the armchair edges are more stable than the
zigzag edges (Okada 2008). However, simulations of
the formation of nanoporous carbons (López et al.
2011) produce more zigzag than armchair edges in the
final structures, what indicates that the formation of
edges is a kinetically controlled process.
We have investigated the adsorption mechanism of
molecular hydrogen on unsaturated zigzag and armchair
edges of graphene nanoribbons. In contrast, with the
weak hydrogen adsorption (physisorption) on a graph-
ene layer or on the surface of carbon nanotubes,
molecular hydrogen interacts strongly with the unsatu-
rated edges of the ribbons, dissociates and chemisorbs
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J Nanopart Res (2012) 14:1263
atomically at the edges. We define the interaction energy
between the hydrogen molecule and the ribbon edge as
Einteraction ¼ Eðribbon þ 2HÞ  EðribbonÞ  EðH2 Þ:
ð4Þ
Figure 2 shows the interaction energy between a
hydrogen molecule and a zigzag edge along a pathway
leading to the dissociation of the molecule without (or
with negligible small) activation barrier. First, the
molecule approaches the ribbon and becomes slightly
activated (H–H distance of 0.089 nm). At a given
distance from the ribbon (0.18 nm), the molecule
begins to dissociate and finally each H atom of the
molecule attaches to a C atom of the edge (adjacent
one to another). Several reaction coordinates are
considered along this path: at long distances, right
hand side panel, the reaction coordinate is the distance
between the molecule and the ribbon, all the other
coordinates are optimized; at intermediate distances,
middle panel, the reaction coordinate is the H–H
distance, and all the other coordinates are optimized
except the distance between the molecule and the
ribbon, that is fixed; at shorter distances, left hand side
panel, the reaction coordinate is the distance between
each H atom and the corresponding edge C atom,
being all the other coordinates optimized. Similarly,
Fig. 3 shows the interaction energy between a hydro-
gen molecule and an armchair edge along a dissocia-
tive pathway without (or with negligible small)
activation barrier. The molecule dissociates at a
distance of 0.13 nm from the edge along this path.
Both the LDA and the PW91-GGA exchange–
correlation functionals have been used to calculate the
interaction energies given in Figs. 2 and 3. The LDA
curves lie below the GGA curves since, as for many
physical systems, the LDA overestimates the cohesive
energy (negative value of the interaction energy),
whereas the GGA tends to underestimate it. The GGA
curves exhibit a small dissociation barrier at distances
of 0.20 and 0.15 nm, for hydrogen adsorption on the
zigzag and armchair edges, respectively. No barrier is
present in the LDA curves. It is worth noticing that at
large distances, when there is no overlap between the
electronic densities, the interaction between the hydro-
gen molecules and the ribbon edges is mainly due to
dispersion forces of the Van der Waals type. Neither
the LDA nor the GGA of the DFT formalism captures
those forces. Therefore, we have corrected the GGA
J Nanopart Res (2012) 14:1263
Fig. 2 Interaction energy of a hydrogen molecule with a zigzag
edge. The selected pathway leads to the dissociation of the
molecule without (or with negligible small) activation barrier.
The reaction coordinate is a the distance between the molecule
and the ribbon on the righthand side panel, all the other
coordinates being optimized; b the H–H distance in the middle
panel, all the other coordinates being optimized except the
distance between the molecule and the ribbon; c the distance
between each H atom and the corresponding edge C atom in the
lefthand side panel, being all the other coordinates optimized
Fig. 3 Interaction energy of a hydrogen molecule with an
armchair edge. The selected pathway leads to the dissociation of
the molecule without (or with negligible small) activation
barrier. The reaction coordinates are the same as in Fig. 2
energies by adding the C6 correction (Wu and Yang
2002) that represents the Van der Waals interaction. As
the hydrogen molecule approaches the ribbon edge, the
electronic densities of these two systems begin to
overlap and the dispersion forces become only a small
fraction of the total interaction energy. The adsorption
energy (negative of the interaction energy given in
Eq. 4 calculated at the minimum) per hydrogen
molecule is 5.65 eV in the zigzag edge and 2.53 eV
in the armchair edge. This shows that the unsaturated
Page 5 of 9
Fig. 4 Density of states (in arbitrary units) of a zigzag ribbon
with unsaturated edges (blue line) and with one adsorbed
hydrogen molecule in one edge (red line). The discrete
eigenvalues obtained in the supercell calculation are broaden
with a Lorentzian function of width 0.05 eV. (Color figure
online)
edges of the ribbons are very reactive and exhibit a
strong tendency to saturate with hydrogen, whenever
available. The edges act as catalysts for the dissocia-
tion of the hydrogen molecule. Upon dissociation, each
hydrogen atom of the molecule saturates a dangling
bond of a C atom of the edge. Since the C atoms of the
edges exhibit sp2 hybridization, the C–H bonds follow
the directions corresponding to the honeycomb struc-
ture of graphene. As a result, the distance between the
two chemisorbed H atoms is smaller in the armchair
edge, 0.194 nm, than in the zigzag edge, 0.241 nm.
The proximity of the two chemisorbed hydrogen atoms
in the armchair edge weakens the C–H bond yielding to
a smaller binding energy than in the case of the zigzag
edge. The higher binding energy of hydrogen to the
zigzag edge is also consistent with the density of states
shown in Fig. 4. The clean zigzag edge has an
electronic gap at the Fermi level which is not destroyed
by adsorption of a hydrogen molecule. An electronic
gap is taken as the signature of a stable system. In
contrast, as it is shown in Fig. 5, the adsorption of a
hydrogen molecule in an armchair edge introduces an
occupied band at the Fermi level, what is the signature
of a weaker C–H bond.
As it is well known, the infinite graphene layer is a
zero gap semiconductor. By applying the zone-folding
model to the graphene electronic bands, it has been
predicted that all the zigzag ribbons are metallic and
one out of three (as a function of width) armchair
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Page 6 of 9
Fig. 5 Density of states (in arbitrary units) of the armchair
ribbon with unsaturated edges (blue line) and with one adsorbed
hydrogen molecule in one edge (red line). (Color figure online)
ribbons is also metallic (Fujita et al. 1996; Nakada
et al. 1996). However, within the more accurate DFT
formalism it is found that all the nanoribbons are small
gap semiconductors. The ribbon formed by six zigzag
chains has a bandgap of 0.82 eV and the ribbon
formed by six armchair chains has a bandgap of
0.29 eV, as calculated using the PW91-GGA func-
tional. Upon adsorption of a hydrogen molecule the
zigzag ribbon remains semiconductor, although with a
smaller gap of 0.75 eV, whereas the armchair ribbon
closes up the gap. Figures 4 and 5 show the density of
states of zigzag and armchair-terminated ribbons,
respectively, with unsaturated edges and with one
adsorbed hydrogen molecule at one edge.
Our PW91-GGA calculations show that the zigzag
ribbons exhibit electronic states around the Fermi level
which are localized at one edge of the ribbon, in
agreement with previous LDA studies (Son et al.
2006a). These localized edge states have opposite spin
orientations at each ribbon edge, giving rise to a total
spin S = 0, that is, there is an antiferromagnetic, AF,
ordering between the net spins at the two edges. The
nonmagnetic (spin non-polarized) state of the ribbon is
2.9 eV/nm higher in energy than the AF ground state.
The presence of molecular hydrogen in the vicinity of a
zigzag edge does not modify the AF magnetic ordering
of the ribbon edges. However, upon hydrogen disso-
ciation/adsorption on the zigzag edge, the spin state of
the ribbon changes to a magnetic state with non-
compensated spins. The two electrons supplied by the
two hydrogen atoms get the same spin orientation and
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J Nanopart Res (2012) 14:1263
opposite to that of the edge states at the adsorbing edge.
Thus, the net spin at the adsorbing edge is reduced in
2 U of spin, whereas it does not experience any change
at the other edge. As a consequence, the ribbon
acquires a magnetic moment of 2 lB per hydrogen
molecule adsorbed on the same edge. Other pathways
for generating magnetism in graphene systems have
been suggested previously in the literature, e.g., in
small nanographene flakes (Fernández-Rosier and
Palacios 2007; Hod et al. 2008), through vacancies or
nanohole superlattices in graphene (Ma et al. 2004; Yu
et al. 2008), and by selective addition of H atoms at one
edge of of H-terminated graphene nanoribbons (Ku-
sakabe and Maruyama 2003). Figure 6 shows the
difference between the spin up and spin down
electronic densities for the zigzag terminated ribbon
(a) with non-saturated edges, (b) with a hydrogen
molecule in the proximity of the edge, and (c) with one
dissociated/adsorbed hydrogen molecule at the edge.
In all cases, the two edges of the ribbon exhibit opposite
spin polarizations, which are compensated in cases
(a) and (b) but is not compensated in case (c) because
the C–H bonds are non-spin-polarized.
Armchair nanoribbons do not exhibit occupied
localized edge states (Son et al. 2006a). However, our
PW91-GGA calculations show that in the proximity
but above the Fermi level there are some empty
localized edge states (see Fig. 7). In contrast with the
zigzag ribbons, these edge states are non-spin-polar-
ized and each state localizes at both edges. Thus, the
ground state electronic structure of the armchair
ribbons is spin non-polarized. The presence of
molecular hydrogen in the proximity of the armchair
edge or the dissociation/adsorption of hydrogen at the
edge does not change the non-polarized state of the
ribbon. However, upon hydrogen adsorption the edge
states become localized at only one edge, and some of
them become occupied edge states (see Fig. 8).
Given the strong tendency of graphene edges to
saturate with hydrogen, whenever available, we have
also investigated the zigzag and armchair ribbons with
fully hydrogen-saturated edges. The saturated zigzag
ribbons exhibit edge states and an AF magnetic ground
state of spin S = 0 similar to the ribbons with exposed
edges. Figure 9 presents the difference between the
spin up and spin down electronic densities of the ribbon
showing clearly the opposite spin polarization of the
two edges. On the other hand, the saturated armchair
ribbons are nonmagnetic as the unsaturated ones.
J Nanopart Res (2012) 14:1263 Page 7 of 9

(a) (b) (c)

Fig. 6 Difference between spin up and spin down electronic and c with one dissociated/adsorbed hydrogen molecule at one
densities of the zigzag terminated ribbon a with unsaturated edge. Blue and red represent the positive and negative
edges, b with a hydrogen molecule in the proximity of the edge, isosurfaces, respectively, of value 0.01 e/au3

Fig. 7 Electronic wave functions of the armchair nanoribbon 0.4375, k2 = 0.3125, k3 = 0.1875, and k4 = 0.0625, all in
with unsaturated edges. HOMO and LUMO states are shown units of p/a, where a = 1.709 nm is the length of the armchair
for several k points of the first Brillouin zone: k1 = supercell used in the calculation

Fig. 8 Electronic wave functions of the armchair nanoribbon at one k-point of the first Brillouin zone, k = 0.21875 p/a,
with one dissociated/adsorbed hydrogen molecule at one edge. where a = 1.709 nm is the length of the armchair supercell used
HOMO - 1, HOMO, LUMO, and LUMO ? 1 states are shown in the calculation

123
Page 8 of 9
Fig. 9 Difference between spin up and spin down electronic
densities of the zigzag ribbon with hydrogen-saturated edges.
Blue and red represent the positive and negative isosurfaces,
respectively, of value 0.01 e/au3. (Color figure online)
However, in contrast with the unsaturated ribbons, all
the states of the hydrogen-saturated ribbons including
the states around the Fermi level are delocalized across
the whole ribbon, there are no states localized at the
edges. This result is in agreement with previous LDA
calculations (Son et al. 2006a). Hydrogen saturation of
the ribbon edges reduces by almost a factor of two the
bandgap of the zigzag edges to a value of 0.42 eV,
whereas the bandgap of the armchair edges increases
by almost a factor of two to the value of 0.53 eV. These
values are in fair agreement with the values of 0.35 and
0.6 eV, respectively, reported using the LDA (Son
et al. 2006a). It is worth noticing that STM images
(Kobayashi et al. 2005) show the edge states in zigzag
edges. However, on the light of the same experiments it
is concluded that the armchair edges do not exhibit
edge states. Most probably in the experiments the
edges are saturated either with hydrogen or with other
species. Our results then fully agree with the STM
experiments.
Summary
We have investigated the adsorption mechanism of
molecular hydrogen on the exposed edges of graphene
nanoribbons with zigzag and armchair terminations on
the basis of the DFT. Nanoribbons are used as models of
the pore walls of nanoporous carbons which consist of
interconnected nanographenes with exposed edges. We
address the question of what is the contribution of the
edges to the hydrogen storage capacity of the material. It
is well known that the adsorption of molecular hydrogen
on graphitic surfaces is driven by weak, Van der Waals
type, interactions. In contrast, we have shown that the
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J Nanopart Res (2012) 14:1263
molecular hydrogen interacts strongly with the edges of
graphene nanoribbons. Hydrogen dissociates without or
with small activation barriers in the proximity of both
zigzag and armchair edges and adsorbs, as atomic
hydrogen, in two adjacent, unsaturated C atoms of the
edge. The adsorption energy is 2.5 and 5.7 eV/molecule
on armchair and zigzag edges, respectively. The strong
binding of hydrogen with the exposed edges of graphene
indicates that the edges readily adsorb hydrogen
whenever available. However, this hydrogen cannot
be released under mild conditions of pressure and
temperature. Therefore, we can conclude that although
the edges of the pore walls of nanoporous carbons will
adsorb hydrogen very easily, they do not contribute to
enhance the reversible hydrogen storage capacity of the
material at room temperature because the adsorbed
hydrogen cannot be released at that temperature.
We have also studied the magnetic properties of
graphene nanoribbons. Zigzag ribbons, both unsaturated
and with hydrogen saturated edges, exhibit edge states
with opposite spin orientation at each edge, antiferro-
magnetic ordering, being the net spin of the ribbon
S = 0. Hydrogen adsorption on only one edge breaks the
compensation of spins between the two edges yielding a
net magnetic moment of the ribbon of 2 lB per adsorbed
hydrogen molecule. This suggests the possibility of
tailoring the magnetic moments in graphitic carbons. On
the other hand, armchair nanoribbons do not exhibit
occupied edge states. The unsaturated ribbons, however,
exhibit some empty states (above the Fermi level) which
are localized at both edges. Localization at a single edge
of occupied and empty states around the Fermi level is
induced by hydrogen adsorption in one edge.
Acknowledgments This study was supported by MICINN of
Spain (Grants MAT2008-06483-C02-01 and MAT2011-22781)
and Junta de Castilla y León (Grant VA158A11-2). IC
acknowledges support from MEC of Spain through the Ramón
y Cajal Program. CB acknowledges support from University of
Valladolid through a Research Starting Program.
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