RESEARCH ARTICLE | JUNE 18 2015

Hybrid molecular simulation of methane storage inside

pillared graphene 
Atieh Hassani; Mohammad Taghi Hamed Mosavian; Ali Ahmadpour; ... et. al

J. Chem. Phys. 142, 234704 (2015)

https://doi.org/10.1063/1.4922541

CrossMark

 
View Export
Online Citation

Articles You May Be Interested In

Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf

Understanding the photonics of single color-center emission in a high-indexed nano-pillar
Journal of Applied Physics (August 2021)

Topology and dynamics of the A-pillar vortex

Physics of Fluids (March 2013)

Raman scattering in GaN pillar arrays

Journal of Applied Physics (March 2002)
 THE JOURNAL OF CHEMICAL PHYSICS 142, 234704 (2015)

Hybrid molecular simulation of methane storage inside pillared graphene

Atieh Hassani, Mohammad Taghi Hamed Mosavian, Ali Ahmadpour,
and Nafiseh Farhadiana)
Chemical Engineering Department, Faculty of Engineering, Ferdowsi University of Mashhad,
Mashhad 9177948974, Iran
(Received 20 December 2014; accepted 3 June 2015; published online 18 June 2015)

In this study, a hybrid molecular dynamics—grand canonical Monte Carlo simulation is carried out to
investigate the storage capacity of methane in a new nanostructure adsorbent called pillared graphene.
This new nanostructure is composed of graphene sheets in parallel with vertical carbon nanotubes
(CNTs), which act as their holders. The adsorption ability of this new structure is compared to
graphene sheets to evaluate its potential for methane storage. The results show that in a specific
adsorbent volume, applying pillared graphene increases the number of adsorbed methane up to
22% in comparison to graphene sheets. Given the application of various isotherm models such
as Langmuir, Freundlich, Sips, and Toth and calculation of their parameters, it is predicted that
methane adsorption on pillared graphene displays a heterogeneous behavior. Furthermore, the effects

Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf

of geometry parameters such as CNTs diameter, the number of CNTs, and graphene sheets layer
spacing on the methane uptake are investigated. The results show that the pillared graphene containing
1 CNT per 30 nm2 graphene sheet areas provides the best configuration for methane adsorption. This
optimum structure is characterized by a small diameter of about 0.938 nm and an optimal layer
spacing of about 1.2 nm. Finally, our results show that this kind of pillared structure can be suitable
for methane storage. C 2015 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4922541]

I. INTRODUCTION
Methane as one of the main constituents of natural gas can
be a good alternative to fossil fuels in terms of energy produc-
tion.1–3 In comparison to other hydrocarbon fuels, methane
produces high energy intensity with low harmful materials
during the combustion process, which makes it a source of
clean energy for gas-fueled vehicles.2,4 Given that methane
has low combustion heat per unit volume and low critical
temperature, applying a high pressure of around 200 bars at
low temperature to store methane as a compressed natural
gas (CNG) has a number of disadvantages such as increased
risk of explosion, expensive design, and manufacturing of fuel
containers. Indeed, it is necessary to develop new adsorbents
materials that are capable of storing methane at a temperature
close to the ambient temperature and lower pressure. For
this purpose, methane needs to be stored in containers with
special adsorbents of medium pressure (about 40 bars) and
low temperature.5,6 Porous carbons, especially the ones with
nanostructure morphology, best serve this goal.7 The porous
materials such as graphene,8,9 carbon nanotubes (CNTs),1,10
various activated carbons,11–18 carbon nanoscrolls,19 mesocar-
bon microbeads,20 coal,21 and fibers22,23 have a high surface to
volume ratio which allows storing greater amounts of methane
at the ambient temperature and lower pressure. Recently, a new
carbon nanostructure material composed of graphene sheets
in parallel with vertical carbon nanotubes as the holder of
graphene sheets has been suggested for gas storage. This new
structure, called pillared graphene, is characterized with light
a)Author to whom correspondence should be addressed. Electronic mail:
n.farhadian@um.ac.ir
weight, stable structure, high volume, and high capacity of gas
storage.24,25 Compared to other nanoporous materials, rapid
transport and self-diffusion of gases in single wall carbon nano-
tube (SWCNT) in a wide range of diameters26,27 are important
criteria that justify the selection of SWCNT as the holder of
graphene sheets. Diffusion in nanotubes with small diameter is
faster than the larger tubes because of higher curvature. This
provides smoother potential energy surface for the interaction
of gas molecules and wall surface. An increase in the length of
nanotube is tantamount to the increased surface resistances.26,28
This structure was first constructed by combining surface catal-
ysis in situ vapor-liquid-solid mechanism in 201029 followed by
applying chemical vapor deposition process in 2011.30 Later,
pillared graphene was produced directly by growing aligned
carbon nanotubes between graphitic layers through pyrolysis
process.31 In 2012, Zhu et al. fabricated CNT–graphene hybrid
in two materials connected by a covalent bond.32 The idea of
applying pillared graphene to gas storage was first theorized
for hydrogen storage.25 Then, in 2010, Grand Canonical Monte
Carlo (GCMC) simulation was applied to predict hydrogen gas
storage inside a pillared graphene oxide doped with lithium
metal at lower pressure and temperature.33 In 2012, Wu et al.
investigated the effect of temperature, pressure, and geomet-
rical structure of pillared graphene on hydrogen adsorption
using molecular dynamics (MD) simulation. Their research
showed that at low temperature, high pressure and larger
interlayer distance between the graphene sheets, applying
pillared graphene, increased the hydrogen storage capacity of
pillared graphene.34 As indicated in the literature, recent studies
are mostly focused on the hydrogen adsorption in pillared
graphene. Methane adsorption at low pressure and temper-
ature is a critical problem in gas-fueled vehicles industry,

0021-9606/2015/142(23)/234704/8/$30.00 142, 234704-1 © 2015 AIP Publishing LLC

234704-2 Hassani et al.
which can be resolved by pillared graphene. According to our
findings, there is not any specific study on methane uptake
inside pillared graphene composed of CNT. However, there are
some experimental researches on methane uptake with similar
pillared configurations and related materials. For example,
Kumar et al. showed that pillared graphene with organic linkers
could be used for methane uptake with remarkable storage
capacity.35 The employment of a graphene-like BxCyNz struc-
ture in another study showed that a remarkable uptake of
methane can be achieved in the new synthesized structure.36
In 2009, Alcañiz-Monge et al. performed some experimental
studies on methane adsorption in a variant type of microporous
carbons at high pressure (up to 40 bars) and a temperature
of 298 K.37 They managed to achieve a methane adsorption
of about 13 mmol/g using a kind of super activated carbon
(K3802). In 2011, the methane adsorption on different types
of granular activated carbon at high pressure was examined
to investigate the adsorption value of applied adsorbents with
various physical characteristics.16 In a study by a group of
researchers in 2012, a type of graphene oxide with high surface
area called graphene oxide derived carbons (GODCs) was
examined for methane storage.38 The experimental results
showed that these materials were good candidates for the
application of gas adsorption. The adsorption of methane in
one form of super activated carbon at various temperatures
was reported in 2013 by Stadie.39 According to their results, an
increase in the temperature reduced the amount of adsorption
value. Recently, studies on the amount of methane storage in
activated carbon with moderate density and high porosity have
revealed that higher porosity can be achieved by increasing
adsorption capacity.40 To the knowledge of the authors, there
are few molecular simulation studies on methane storage in
pillared graphene composed of CNT, and there is a paucity
of experimental data in this area. To fill this gap, this study
seeks to assess the ability of pillared graphene in methane
adsorption using molecular simulation method. As such, a new
hybrid simulation containing molecular dynamics simulation
and Monte Carlo (MC) simulation was applied to achieve this
goal. Also, the effects of some important operating parameters
such as temperature and pressure as well as some structural
parameters such as CNTs numbers, diameter, and graphene
sheet layer spacing on the adsorption capacity were examined.
II. COMPUTATIONAL DETAILS
A hybrid molecular simulation is performed to predict
methane adsorption on pillared graphene. Simulations are
FIG. 1. Schematics of (a) two parallel graphene sheets and (b) pillared graphene with two carbon nanotubes.
J. Chem. Phys. 142, 234704 (2015)
performed at two different stages. In stage 1, simulations
are setup to compare the amount of adsorbed methane on
graphene sheets and pillared graphene. In stage 2, the effect
of operating parameters such as pressure and temperature as
well as morphology parameters such as graphene sheets layer
spacing, the number of CNTs, and CNTs diameter on the
amount of adsorbed methane is investigated.
A. System configuration
1. Part 1
The system is composed of two parallel graphene sheets
with a length, width, and distance of 10, 6, and 1.75 nm, respec-
tively. Pillared graphene is constructed on the same configura-
tion by adding two zigzag CNTs (18, 0) with a diameter of
1.43 nm located at a distance of 2 nm from each other. CNTs
are assumed pure, ideal with an open-ended structure, and
Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf
unaffected by gas adsorption. According to the literature,41–44
the flexibility of CNT can affect the adsorption amount of
gases, especially at low pressure (P < 1 bar). In this study,
since all applied pressures are above 1 bar, the effect of flex-
ibility on the adsorbed methane amount would be negligible.
Indeed, both graphene sheets34,45 and CNT are rigid structures.
The cell is cubic in form with 14 × 10 × 10 nm dimensions.
Figure 1 shows system configurations for both graphene and
pillared graphene sheets.
2. Part 2
In this part, some configuration parameters of pillared
graphene such as the layer spacing between sheets, CNT
diameter, and the number of CNTs have been changed. The
previous experimental studies on methane adsorption inside
graphene suggest that the best layer spacing to yield the
maximum amount of adsorbed methane is in the range of
0.68–2.04 nm.45 Thus, our system consisted of two graphene
sheets, with the graphene layer distance (or CNT length)
varying from 0.8 to 1.75 nm to obtain three configurations
(layer spacing of 0.8, 1.2, and 1.75 nm). The best layer dis-
tance from these configurations will be selected later. In other
configurations, CNTs’ diameters are modified from 0.938 to
2.345 nm (CNTs diameters: 0.938, 1.43, and 2.345 nm) with
a constant layer spacing of 1.75 nm. The selected values for
CNTs diameter are taken from previous studies on methane
storage in CNTs.4,19,28,46,47 In the last set of configurations,
pillared graphene is constructed with one, two, and four CNTs
with a diameter of 1.43 nm and a layer spacing of 1.75 nm for
234704-3 Hassani et al.
FIG. 2. Schematics of primary structures of pillared-graphene with different distances of two graphene sheets (a) 0.8 nm, (b) 1.2 nm, and (c) 175 nm.
FIG. 3. Schematics of primary structures of pillared graphene with different CNTs diameters (a) 0.938 nm, (b) 1.43 nm, and (c) 2.345 nm.
graphene sheets. Figures 2–4 show the schematics of applied
configurations.
B. Simulation method
A hybrid Molecular Dynamics-Monte Carlo (MD-MC)
simulation is carried out to compute the storage capacity and
adsorption isotherm of methane molecules on the graphene
and pillared graphene sheets. To do so, the adsorption iso-
therms are calculated by a grand canonical ensemble created
by combining MD and MC steps. Two control volumes (CVs)
were placed on the top and bottom of the above-mentioned
structures, where the adsorbate and the bulk phase were in
balance at a constant pressure (Fig. 5). The Nosé–Hoover–
Langevin pistons at both ends keep the pressure or chemical
potentials constant. This method is based on the GCMC tech-
nique in which MD algorithm is applied to simulate the move-
ment of atoms. This method was successfully applied to deter-
mine the adsorption capacity of carbon dioxide, hydrogen, and
methane gases in the CNT by Sahimi and Malek.48
Simulations are performed for a range of pressures vary-
ing from 1 to 44 bars. The insertion-deletion process is, respec-
tively, implemented according to Eqs. (1) and (2) to keep the
densities of CVs constant,
 
ZiV
p+ = min 1, exp −∆U +/k BT ,


Ni + 1
 
Ni
p− = min 1, exp −∆U −/k BT ,


ZiV
where ∆U is potential energy variation caused by addition
±
or elimination of one molecule, Zi is the absolute fugacity
at the temperature T,V is the volume of CVs, Ni is the
FIG. 4. Schematics of primary structures of pillared graphene with different CNTs: (a) 1CNT, (b) 2CNTs, (c) 4CNTs.
J. Chem. Phys. 142, 234704 (2015)
Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf
number of atoms of gas i, and k B is Boltzmann’s constant.
To convert fugacity to pressure, the compressibility factor of
methane gas is used. The time interval (∆t) for addition and
elimination of consecutive processes is assumed 50–150 ps.
Leapfrog integration is used to calculate Newton’s equation
of motion, and LINCS algorithm is applied to demonstrate
the physical constraints of the molecules.48 The tempera-
ture is kept constant at 298 K using Berendsen thermostat.
Maxwell–Boltzmann distribution is applied to determine the
velocity of central molecular mass inserted randomly in their
position. Gromacs software is used to simulate the movement
of methane molecules in the box through MD simulation.49
Adsorbents (graphene and pillared graphene) are assumed
frozen in all x, y, and z axes. Methane molecules are assumed
as spherical molecules with zero net charge. Therefore, only
Lennard-Jones (LJ) potential is employed for intermolecular
forces calculations as follows:
 ( σ ) 12 ( σ ) 6
ij ij 
U(r i j ) = 4ε  − , (3)
 r i j r i j 

where σij and εij are the Lennard-Jones size and energy param-
eters, respectively. The Lorentz-Berthelot rules have been used
to calculate sigma and epsilon according to Eqs. (4) and (5),
(1)
1
σi j = σii + σ j j , (4)


2
(2)

1
ε i j = ε ii ε j j 2 . (5)
The Lennard-Jones parameters employed for methane and
carbon atoms of adsorbents are listed in Table I.49,50
234704-4 Hassani et al. J. Chem. Phys. 142, 234704 (2015)

TABLE I. Lennard Jones parameters for different interactions of intermolec-

ular pairs.

Pair ε (kcal/mol) σ (Å) Reference

CH4–CH4 0.294 3.817 50

C–C 0.0969 3.36 49

CH4–C 0.1687 3.5885

methane inside CNTs has been shown from the top view. As
can be seen, methane molecules form a single adsorbed layer
inside CNTs.
To illustrate the adsorption mechanism of methane mole-
cules on the adsorbents, the amount of adsorbed methane
(nadsorbed methane/madsorbent) as a function of the pressure has
been plotted in Figure 7. As can be seen, at low pressure (P
< 3bars), the amount of adsorbed methane on pillared graphene

Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf

FIG. 5. Constant pressure maintained throughout the simulated configura-
is approximately the same as graphene sheets. In systems with
tions. a pressure above 3 bars, the number of adsorbed methane on
pillared graphene is higher than that of graphene sheet. This
can be enhanced up to 22% in pressures as high as 40 bars.
III. RESULTS AND DISCUSSION
Overall, the rate of methane adsorption versus pressure is an
incremental process in both structures.
A. Methane adsorption on the graphene and pillared
graphene systems
B. Modeling of adsorption mechanism
At first, it is necessary to compare the amount of ad-
sorbed methane on the graphene and pillared graphene sheets. To model methane adsorption on graphene and pillared
Figure 6 shows some snapshots of the methane adsorption graphene, four common types of isotherm models, i.e., Lang-
on two parallel graphene sheets and a pillared graphene after muir,51 Freundlich,52 Sips,53 and Toth,54 are used. Equations
reaching equilibrium at a pressure of 44 bars. As can be seen, (6)–(9) show the applied forms of these equations, respec-
methane molecules are adsorbed on the inner and outer layers tively,
of graphene sheets in both configurations, forming a single Langmuir isotherm model:
layer on the graphene sheets. In the pillared graphene structure, 1 1 1 1
methane molecules are adsorbed on the internal surface of = + , (6)
Cµ Cµs bCµs P
CNTs rather than its outer surface. This could be due to the
CNT curvature and higher van der Waals interactions inside Freundlich isotherm model:
CNT in comparison to the CNT outer surface. For ease of 1
comprehension, in Figure 6(c), the schematic of the adsorbed log10 (Cµ) = log10 (k) + log10 (P) , (7)
n

FIG. 6. Snapshots of methane adsorption at a pressure of 44 bars and a temperature of 298 K for (a) two parallel graphene sheets, (b) pillared graphene, (c) top
view of pillared graphene.
234704-5 Hassani et al. J. Chem. Phys. 142, 234704 (2015)

FIG. 7. Isotherm of the adsorbed methane on graphene sheets and pillared FIG. 8. Adsorption amount of methane on the pillared graphene at a pressure
graphene. of 5 bars.

Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf

Sips isotherm model:
(bP)1/n
Cµ = Cµs , (8)
1 + (bP)1/n
Toth isotherm model:
bP
Cµ = Cµs , (9)
[1 + (bP)t]1/t
where Cµ is the amount of adsorbed molecules (mole per unit
mass or volume) and Cµs is the maximum amount of adsorbed
molecules required to form complete monolayer coverage. In
Langmuir equation, b is the affinity constant which acts as
a measure of adsorbate-adsorbent attraction forces. In Fre-
undlich model, n and k are the adsorption capacity and inten-
sity, respectively. Finally, n in Sips equation and b in Toth
equation characterize the system heterogeneity. According to
Eqs. (6) and (7), the linear form of Langmuir and Freundlich
models has been incorporated in calculations. Figures S1(a)
and S1(b) presented in the supplementary material55 show the
results for these two isotherm models. The equation param-
eters can be calculated based on the slope of the linear curve
and the intercept. The normal forms of Toth and Sips equations
have been applied. Supplementary55 Figures S1(c) and S1(d)
show the curve fitting for calculating related parameters. All
parameters calculated for four equations are shown in Table II.
According to Table II, the adsorbed amount of gas molecules
on the pillared graphene is larger than that of graphene sheets
(Cµs,pillared > Cµs,graphene and npillared > ngraphene > 1). More-
over, the parameters calculated in Sips (n) and Toth (t) models
confirm that methane adsorption on pillared graphene is more
heterogeneous than that of graphene sheets. When parameter
n in Sips model is greater than 1 and parameter t in Toth model
is smaller than 1, the heterogeneity of system will be high.56
This may be due to the CNTs’ presence in the pillared graphene
structure with higher curvature properties in comparison to the
graphene sheet.
C. Effect of temperature
To investigate the impact of temperature on the adsorption
process, the adsorption amounts of methane molecules versus
temperature were plotted at a pressure of 5 bars (Fig. 8). As
Figure 8 shows, an increase in the temperature reduces the
adsorption amount of gas molecules. In other words, increased
temperature accelerates the movement and collision of gas
molecules, therefore increasing the desorption rate of the ad-
sorbed molecules.
D. Effect of pillared graphene geometry
on the adsorption
As discussed earlier, it can be concluded that the adsorp-
tion ability of pillared graphene is greater than that of graphene
sheets. Moreover, the new structure has higher mechanical
stability than other carbonous materials such as graphene.24,57
Hence, investigating the effect of important morphological
parameters on adsorption may help select the best configura-
tion for methane storage. For this purpose, the effect of CNT
diameters, the number of CNTs, and graphene sheets’ layer
spacing on the methane adsorption are examined. In Figure
S2 of the supplementary material,55 the simulated structures
after methane adsorption has been shown. The isotherm curves
for all three configuration sets are shown in Figure 9. As
can be seen, for all selected configurations at low pressure
(P < 10 bars), there is not any significant difference between

TABLE II. Adsorption isotherm parameters for Langmuir, Freundlich, Sips, and Toth models.

Langmuir Freundlich Sips Toth

Type Cµs b R2 k n R2 Cµs b n Cµs b t

Graphene 15.823 0.047 0.997 0.801 1.295 0.994 50.051 0.007 1.200 52.432 0.012 0.570
Pillared 32.051 0.023 0.997 0.887 1.299 0.986 64.757 0.004 1.367 73.641 0.015 0.479
234704-6 Hassani et al.
FIG. 9. Comparison of methane adsorption isotherms in the pillared
graphene for different CNT diameters (a), layer spacing (b), and number of
CNTs (c).
the adsorption amounts of methane. With an increase of more
than 10 bars in the pressure, the amounts of adsorbed methane
for various configurations are changed. By decreasing CNT
diameters, the available surface area of graphene sheets and
the curvature of CNT is increased, which in turn enhances the
amounts of adsorbed methane. For layer spacing, there is an
J. Chem. Phys. 142, 234704 (2015)
optimum distance at which the maximum methane adsorption
can be achieved. When two layers of graphene sheets are very
close to each other (d < 0.8 nm), one layer of the adsorbed
methane is produced, which decreases the adsorption amounts
of gas molecules. At a distance of 1.2 nm, however, two
layers of adsorbed methane can be formed between graphene
sheets, thus increasing the amounts of adsorbed methane.
With an increase in the layer spacing (d > 1.2 nm), two
layers of adsorbed methane are generated, but the diminished
interactions of adsorbed molecules and graphene sheets reduce
the adsorption amounts of methane molecules. The above
observations are in agreement with experimental studies. Ac-
cording to Chen et al., isosteric heat of adsorption as a function
of pressure affects the strength of forces between adsorbent
and adsorbed molecules. By increasing the interlayer distance,
the isosteric heat of methane adsorption in graphene sheet
decreases. For graphene layers with a layer distance of more
Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf
than 1.75 nm, this reduction is so high that decreases the
adsorption amount of methane.45 According to Figure 9(c),
the isotherm curve of pillared graphene with two CNTs has
a sharp slope versus pressure. This is evident in schematic S3
of the supplementary material55 where the maximum adsorp-
tion amounts of methane gas at higher pressure are achieved
for 2 CNTs. However, at the pressure between 3 and 44
bars, there is not any significant difference between methane
uptake on pillared graphenes with 2 or 4 CNTs. Accord-
ingly, it can be concluded that the best number of CNTs
in pillared graphene to obtain uptake maximum available
of adsorbed methane is 1 CNT per 30 nm2 graphene sheet,
which is due to the optimal balance between the curvature
of CNT surface and flat surface available to the graphene
sheets. To shed further light on this point, different isotherm
models of Langmuir, Freundlich, Sips, and Toth are applied to
various configurations. The parameters calculated for all sys-
tems are given in Table III, and the fitted plots are shown in the
attachments (see S4, S5, and S6 in supplementary material55).
According to the parameters shown in Table III, a pillared
graphene with two CNTs, a diameter of 0.938 nm, and a layer
spacing of 1.2 nm provide the best structure for methane
adsorption.
Given the paucity of information on methane storage
in the pillared graphene, a comparison was drawn between
the amount of adsorbed methane on the structure examined
in this study and other theoretical and experimental carbon
structures reported in the literatures (Table IV). According to
Table IV, compared to other related carbon structures such
as CNTs and graphene in separate forms, the amount of
methane adsorption in pillared graphene is acceptable with
the same order of value,1,19,58,59 though the adsorption amount
of pillared graphene is higher. Also, pillared graphene can
increase the adsorption amounts of methane more than other
carbonous structures such as cryogel,14 various activated car-
bons,16,39,40,60,61 micro porous carbons,37,62 covalent organic
frameworks (COFs),63 GODCs,38 and graphene-like Borocar-
bonitrides (BxCyNz).36 A comparison of the adsorbed amount
of methane inside pillared graphene composed of SWCNT
with the pillared configurations composed of other materials35
shows that pillaring graphene with SWCNT has a remarkable
effect on the methane uptake.
234704-7 Hassani et al. J. Chem. Phys. 142, 234704 (2015)

TABLE III. Adsorption isotherm parameters for Langmuir, Freundlich, Sips, and Toth models.

Isotherm model Langmuir Freundlich Sips Toth

Parameter Cµs b R2 k n R2 Cµs b n Cµs b t

Diameter (nm)
0.938 35.842 0.020 0.993 0.885 1.311 0.982 67.995 0.003 1.370 75.91 0.014 0.471
1.43 32.051 0.023 0.997 0.887 1.299 0.986 64.757 0.004 1.367 73.641 0.015 0.479
2.345 31.446 0.024 0.997 0.911 1.301 0.986 62.005 0.004 1.364 71.435 0.016 0.496

Layer spacing (nm)

0.8 86.217 0.008 0.996 0.974 1.269 0.973 91.182 0.003 1.400 98.949 0.014 0.447
1.2 120.48 0.009 0.998 0.904 1.192 0.983 130.09 0.002 1.429 130.12 0.012 0.421
1.75 32.051 0.023 0.997 0.887 1.299 0.986 64.757 0.004 1.367 73.641 0.015 0.479

Number of CNTs
1CNT 18.692 0.042 0.997 0.874 1.308 0.992 55.535 0.006 1.290 65.020 0.017 0.500
2CNT 32.051 0.023 0.997 0.887 1.299 0.986 64.757 0.004 1.367 73.641 0.015 0.479
4CNT 21.881 0.036 0.999 0.875 1.282 0.990 57.240 0.005 1.319 70.295 0.016 0.497

Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf

TABLE IV. Summary of the amount of methane storage in different carbon-based materials.

Storage material Experiment (mmol/g) Theoretical analysis (mmol/g)

Carbon cryogel 13 (at 40 bars and room temperature)14

Microporous carbons (K3802) 13 (at 40 bars and 298 K)37
Micro porous carbon (MCB-48P) 15.8 (at 40 bars and 298 K)62
3D covalent organic frameworks (COFs) 13 (at 40 bars and 298 K)63 13.71 (at 40 bars and 298 K) (GCMC)63
Granular activated carbons ∼8 (at 40 bars and 294 K)16
Super activated carbon (MSC–30) 13 (at 40 bars and 298 K)39
Activated carbon 11 (at 30 bars and 298 K)40
Activated carbon fibers 9.35 (at 40 bars and 298 K)60 9.35 (at 40 bars and 298 K) (GCMC)60
Coal-based activated carbon (BPL) 5 (at 40 bars and 301.4 K)61 5 (at 40 bars and 301.4 K) (GCMC)61
Multi wall carbon nanotubes (MWCNTs) 2.1 (at 40 bars and 298 K)1
Carbon nanoscrolls 12.1 (at 40 bars and 298 K) (GCMC)19
Slit-like nanoporous carbon 7 (at 40 bars and 298.15 K) (GCMC)58
Graphite 1.56 (at 10 bars and 298 K)59 1.56 (at 10 bars and 298 K) (modeling)59
Graphene oxide derived carbons (GODCs) (GODCsol-800) ∼11.22 (at 40 bars and 300 K)38
Porous graphene frameworks pillared by organic linkers ∼3.1 (at 1 bar and 195 k)35
Graphene-like borocarbonitrides (BxCyNz) 7.81 (at 40 bars and 298 K)36
Pillared graphene 16.85 (at 40 bars and 298 K) (this study)

E. Calculation of DOE target

With the purpose of using methane gas in vehicles, the
U.S. Department of Energy (DOE) has set a value of 180
V(STP)/V (a standard temperature of 298 K, a pressure of
1.01 bars, and an equivalent volume of methane per volume
of the adsorbent material) for methane storage at a pressure
of 35 bars at the ambient temperature.45 Recently, this value
has been set at 263 V(STP)/V.64 For the structures used in
this study, DOE parameters were calculated and the results are
shown in Figure 10. As can be seen, pillared graphenes with
a layer spacing of 0.8 and 1.2 nm, 2 CNTs, and a diameter of
1.43 nm meet the requirements of the previous DOE value and
are very close to the new value. With the application of these
nanostructures, the methane uptake can reach the prior DOE
standard even at a pressure as low as 35 bars (approximately,
at a pressure range of 25–30 bars). Given the fact that methane
molecule has high polarizability with no polarity, adsorbents
with high specific surface area-like pillared graphene could be FIG. 10. Comparison of adsorption isotherms of methane in two parallel
good candidates for its adsorption.64 graphene layers and different geometries of pillared graphene at 298 K.
234704-8 Hassani et al.
IV. CONCLUSIONS
In this study, the methane adsorption on graphene and pil-
lared graphene sheets was investigated using hybrid molecular
dynamics-Monte Carlo simulation method. The results show
that the application of pillared graphene rather than graphene
sheets enhances the adsorption of methane at a pressure of
about 40 bars by approximately 22%. A variety of isotherms
such as Langmuir, Freundlich, Sips, and Toth models suggests
that methane adsorption can display a heterogeneous behavior
on graphene and pillared graphene sheets. This heterogeneity
in pillared graphene is higher than that of graphene sheets,
which is due to the presence of the CNTs in its structure.
Graphene sheet layer spacing (or CNT length) has the greatest
effect on the adsorption amount of methane among geomet-
rical parameters such as CNT diameter, graphene sheet layer
spacing, and the number of CNTs. According to the results,
it is possible to approximate the methane uptake set in DOE
standard by applying a pillared graphene with specific charac-
terizations.
1M. Rasoolzadeh, S. Fatemi, M. Gholamhosseini, and M. A. Moosaviyan,
Iran. J. Chem. Chem. Eng. 27, 127 (2008).
2P. Kowalczyk, L. Solarz, D. Do, A. Samborski, and J. MacElroy, Langmuir
22, 9035 (2006).
3A. Yamashita, Y. Mori, T. Oshima, and Y. Baba, Carbon 76, 469 (2014).
4S. Vela and F. Huarte-Larrañaga, Carbon 49, 4544 (2011).
5J. Alcaniz-Monge, M. De La Casa-Lillo, D. Cazorla-Amorós, and A.
Linares-Solano, Carbon 35, 291 (1997).
6D. Lozano-Castello, J. Alcaniz-Monge, M. De la Casa-Lillo, D. Cazorla-
Amorós, and A. Linares-Solano, Fuel 81, 1777 (2002).
7C. Solar, A. G. Blanco, A. Vallone, and K. Sapag, in Natural Gas, edited by
P. Potocnik (InTech, 2010), Vol. 205.
8C. Thierfelder, M. Witte, S. Blankenburg, E. Rauls, and W. Schmidt, Surf.
Sci. 605, 746 (2011).
9K. Mosher, J. He, Y. Liu, E. Rupp, and J. Wilcox, Int. J. Coal Geol. 109-110,
36 (2013).
10S. Monemtabary, M. S. Niasar, M. Jahanshahi, and A. A. Ghoreyshi, IJEE
4, 17 (2013).
11S. Himeno, T. Komatsu, and S. Fujita, J. Chem. Eng. Data 50, 369 (2005).
12A. Azimi and M. Mirzaei, World Appl. Sci. J. 17, 1109 (2012).
13P. Ning, F. Li, H. Yi, X. Tang, J. Peng, Y. Li, D. He, and H. Deng, Sep. Purif.
Technol. 98, 321 (2012).
14S. L. Candelaria, Y. Shao, W. Zhou, X. Li, J. Xiao, J.-G. Zhang, Y. Wang, J.
Liu, J. Li, and G. Cao, Nano Energy 1, 195 (2012).
15M. A. Kumar, Master thesis, National Institute of Technology, Rourkela,
2011.
16M. H. Y. Wang, C. Ercan, A. Khawajah, and R. Othman, Catalysts in
Petroleum Refining and Petrochemicals (King Fahd University of Petroleum
and Minerals, Dhahran, Saudi Arabia, 2011).
17M. Sudibandriyo, IJET-IJENS 11, 79 (2011).
18G. Rychlicki, A. P. Terzyk, and J. Zawadzki, Pol. J. Chem. 69, 1328 (1995).
19X. Peng, J. Zhou, W. Wang, and D. Cao, Carbon 48, 3760 (2010).
20X. Shao, W. Wang, R. Xue, and Z. Shen, J. Phys. Chem. B 108, 2970 (2004).
21J. Zhang, M. Clennell, D. Dewhurst, and K. Liu, Fuel 122, 186 (2014).
22S. Jiang, J. A. Zollweg, and K. E. Gubbins, J. Phys. Chem. 98, 5709 (1994).
23D. Lozano-Castello, D. Cazorla-Amoros, and A. Linares-Solano, Energy
Fuel 16, 1321 (2002).
24G. E. Froudakis, Mater. Today 14, 324 (2011).
25G. K. Dimitrakakis, E. Tylianakis, and G. E. Froudakis, Nano Lett. 8, 3166
(2008).
J. Chem. Phys. 142, 234704 (2015)
26A. I. Skoulidas, D. M. Ackerman, J. K. Johnson, and D. S. Sholl, Phys. Rev.
Lett. 89, 185901 (2002).
27H. Chen and D. S. Sholl, J. Membr. Sci. 269, 152 (2006).
28D. A. Newsome and D. S. Sholl, Nano Lett. 6, 2150 (2006).
29R. K. Paul, M. Ghazinejad, M. Penchev, J. Lin, M. Ozkan, and C. S. Ozkan,
Small 6, 2309 (2010).
30M. Ghazinejad, S. Guo, R. K. Paul, A. S. George, M. Penchev, M. Ozkan,
and C. S. Ozkan, Materials Research Society (Cambridge University Press,
2011).
31F. Du, D. Yu, L. Dai, S. Ganguli, V. Varshney, and A. Roy, Chem. Mater. 23,
4810 (2011).
32Y. Zhu, L. Li, C. Zhang, G. Casillas, Z. Sun, Z. Yan, G. Ruan, Z. Peng, A.-R.
O. Raji, and C. Kittrell, Nat. Commun. 3, 1225 (2012).
33E. Tylianakis, G. M. Psofogiannakis, and G. E. Froudakis, J. Phys. Chem.
Lett. 1, 2459 (2010).
34C.-D. Wu, T.-H. Fang, and J.-Y. Lo, Int. J. Hydrogen Energy 37, 14211
(2012).
35R. Kumar, V. M. Suresh, T. K. Maji, and C. Rao, Chem. Commun. 50, 2015
(2014).
36N. Kumar, K. Subrahmanyam, P. Chaturbedy, K. Raidongia, A. Govindaraj,
K. P. Hembram, A. K. Mishra, U. V. Waghmare, and C. Rao, ChemSusChem
4, 1662 (2011).
Downloaded from http://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/1.4922541/15496668/234704_1_online.pdf
37J. Alcañiz-Monge, D. Lozano-Castelló, D. Cazorla-Amorós, and A. Linares-
Solano, Microporous Mesoporous Mater. 124, 110 (2009).
38G. Srinivas, J. Burress, and T. Yildirim, Energy Environ. Sci. 5, 6453 (2012).
39N. P. Stadie, Ph.D. thesis, California Institute of Technology, 2013.
40J. P. Marco-Lozar, M. Kunowsky, J. D. Carruthers, and Á. Linares-Solano,
Carbon 76, 123 (2014).
41H. Chen and D. S. Sholl, J. Am. Chem. Soc. 126, 7778 (2004).
42S. Jakobtorweihen, M. Verbeek, C. Lowe, F. Keil, and B. Smit, Phys. Rev.
Lett. 95, 044501 (2005).
43H. Chen, J. K. Johnson, and D. S. Sholl, J. Phys. Chem. B 110, 1971
(2006).
44A. I. Skoulidas, D. S. Sholl, and J. K. Johnson, J. Chem. Phys. 124, 054708
(2006).
45J.-J. Chen, W.-W. Li, X.-L. Li, and H.-Q. Yu, Environ. Sci. Technol. 46,
10341 (2012).
46D. Cao, X. Zhang, J. Chen, W. Wang, and J. Yun, J. Phys. Chem. B 107,
13286 (2003).
47P. A. Denis, Chem. Phys. 353, 79 (2008).
48K. Malek and M. Sahimi, J. Phys. Chem. 132, 014310 (2010).
49D. van der Spoel, E. Lindahl, B. Hess, A. R. van Buuren, E. Apol, P. J.
Meulenhoff, D. P. Tieleman, A. Sijbers, K. A. Feenstra, and R. van Drunen,
Gromacs User Manual version 4.5.4, www.gromacs.org (2010).
50F. Cuadros, I. Cachadina, and W. Ahumada, Mol. Eng. 6, 319 (1996).
51I. Langmuir, J. Am. Chem. Soc. 38, 2221 (1916).
52H. M. F. Freundlich, J. Phys. Chem. 57, 385 (1906).
53R. Sips, J. Chem. Phys. 16, 490 (1948).
54J. Toth, Acta Chem. Acad. Hung. 69, 311 (1971).
55See supplementary material at http://dx.doi.org/10.1063/1.4922541 for
fitting of adsorption data for Langmuir, Sips, and Toth models and
snapshots of methane adsorption on pillared graphene after reaching
equilibrium.
56O. Moradi, in Thermodynamics–Interaction Studies–Solids, Liquids and
Gases, edited by J. C. M. Piraján (InTech, 2011), Vol. 201.
57R. Kamaliya, B. P. Singh, B. K. Gupta, V. N. Singh, T. K. Gupta, R. Gupta,
P. Kumar, and R. B. Mathur, Carbon 78, 147 (2014).
58S. Yeganegi and F. Gholampour, Adsorption 19, 979 (2013).
59O. O. Adisa, B. J. Cox, and J. M. Hill, Carbon 49, 3212 (2011).
60X. Shao, W. Wang, and X. Zhang, Carbon 45, 188 (2007).
61J. Palmer, J. Brennan, M. Hurley, A. Balboa, and K. Gubbins, Carbon 47,
2904 (2009).
62X. Chen, B. McEnaney, T. Mays, J. Alcaniz-Monge, and A. Linares-Solano,
Carbon 35, 1251 (1997).
63J. Lan, D. Cao, and W. Wang, Langmuir 26, 220 (2009).
64S. Gadipelli and Z. X. Guo, Prog. Mater. Sci. 69, 1 (2015).