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Applied Surface Science 459 (2018) 693–699

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Adsorption and dissociation of CH4 on graphene: A density functional theory T


Kun Li, Hejun Li , Ningning Yan, Tiyuan Wang, Zhigang Zhao
State Key Laboratory of Solidification Processing, Carbon/Carbon Composites Research Center, Northwestern Polytechnical University, Xi'an 710072, China


Keywords: To investigate the mechanism of the heterogenous reactions during the Chemical vapor infiltration (CVI) process
CH4 of carbon/carbon composites, the dissociation of CH4 on graphene was calculated by density functional theory
Dissociation (DFT). Graphene was used as the adsorption surface in the course of the heterogenous reactions. Based on the
Graphene energy analysis, the preferred adsorption sites of CHx(x = 0–4) and H on graphene were obtained. Then, the
Density functional theory
stable co-adsorption configurations of CHx/H(x = 0–3) on graphene were located. The calculation results show
that CH4, CH3 and H prefer to be adsorbed at the top of a carbon atom of graphene, while CH2, CH and C are
favorable on the midpoint of a CeC bond of graphene. Transition state (TS) calculation shows that the dis-
sociation of CH4 into CH3 and H is a rate-determining step. Additionally, by comparing the dissociation of CH3
into CH2 and H and the formation of C2H6 during the dissociation of CH4, it is obvious that the CH3 groups are
more likely to produce ethane rather than dissociating into CH2 and H.

1. Introduction describe the pyrocarbon deposition and gas phase chemistry that is
based on the Langmuir–Hinshelwood kinetics. Lacroix et al. [14], de-
Carbon/carbon (C/C) composites materials are widely used in veloped a heterogenous mechanism to describe the surface reactions of
aerospace and other fields because of their excellent thermal and me- the pyrocarbon deposition using propane on carbon fibers. It showed
chanical properties, like high specific strength, high specific modulus, that the simulation results were in good agreement with the experi-
good fracture toughness and wear resistance at high temperature [1–4]. mental results for both the gas phase composition and deposition ki-
Chemical vapor infiltration (CVI) is one of the most important methods netics.
to produce C/C composites [5–7], which usually uses hydrocarbons as As mentioned above, although there are many detailed studies
carbon precursor, such as methane [8–10]. And methane will be dis- about the mechanism of the CVI process, there is no report on hetero-
sociated under such high temperature and other specific conditions of genous reactions from the atomic level. Even though there are indeed
CVI. During the formation of C/C composites, there are many kinds of lots of research about the adsorption and dissociation of the hydro-
molecules, radicals and carbon species formed by heterogenous reac- carbon molecules (like methane) on metals [15–20], while the de-
tions [11]. Therefore, it is essential to understand the heterogenous position on carbon materials has never been considered. For example,
reactions involved in pyrocarbon deposition, which will help to opti- Wang et al. [21] investigated the dehydrogenation of CH4 on Rh(1 1 1),
mize the CVI process of C/C composites. Rh(1 1 0) and Rh(1 0 0) surfaces, and elucidated the favorable adsorp-
A lot of work has been performed by researchers to study the me- tion sites and dehydrogenation mechanism of CH4. Zhang et al. [22]
chanism of CVI process. Li et al. [12], proposed a model in which investigated the adsorption and dissociation of CH4 on Pt(h k l) surfaces
acetylene, ethylene and benzene were used as the carbon precursors to using Density Functional Theory (DFT) method.
explain the elementary reaction mechanism of the CVI process. In this Recently, graphene has been widely studied for its fundamental
model, a lumped surface reaction mechanism was put forward, and the aspects and other applications, such as the thermal transport property
data of the surface reactions was acquired by combining the experi- [23,24] and catalysis [25]. In this study, graphene was used as the
mental results and simulated results. Becker and Huttinger [13] used adsorption surface during the heterogenous reactions. Because the
active surface sites to analyze the deposition reactions including ad- atomic structures of the carbon fibers and the deposited pyrocarbon in
sorptions, surface reactions and desorption. This is the first model to the C/C composites are both turbostratic graphite structure [26–28],

Corresponding author.
E-mail address: (H. Li).
Received 26 April 2018; Received in revised form 18 July 2018; Accepted 7 August 2018
Available online 09 August 2018
0169-4332/ © 2018 Elsevier B.V. All rights reserved.
K. Li et al. Applied Surface Science 459 (2018) 693–699

and graphene is a typical single layer graphite, to simplify the calcu-

lation, it is reasonable to consider graphene as the ideal microstructure
of the adsorption surface. Methane was used as the carbon precursor
gas. The sequential dehydrogenation of CH4 on graphene was in-
vestigated and the formation of C2H6 during the dissociation of CH4 was
compared with the dissociation of CH3 into CH2 and H. Besides, the
adsorption configurations of CHx(x = 0–4) and H on graphene and the
co-adsorption configurations of CHx/H(x = 0–3) on graphene were
calculated. Due to the complexity of the heterogenous reactions, this
study discusses the adsorption and dissociation of CH4 on graphene.

2. Computational details

2.1. Method

All the calculation of the density functional theory was performed

using Dmol3 [29,30] module implemented within the Materials Studio
of Accelrys, Inc [31]. The electron exchange and correlation interac-
tions were described by the Perdew-Burke-Ernzerhof (PBE) function
within the generalized gradient approximation (GGA) [32]. The k-point Fig. 1. Top view and side view of methane adsorbed on three sites of graphene:
meshes for Brillouin zone sampling were sampled with a 3 × 3 × 1 bridge site, center site and top site. C and H atoms are shown in the grey and
white colors, respectively.
Monkhorst-Pack grid. The convergence criteria for structure optimiza-
tion were set to 1.0 × 10−6 eV/atom, 1.0 × 10−5 eV/atom,
2.0 × 10−3 Ha/Å and 5.0 × 10−3 Å for the tolerance of SCF (self-con- Table 1
sistent field), energy, maximum force, and maximum displacement, The calculated adsorption energies (Eads ) and structural parameters for
respectively. The double-numeric quality basis set with polarization CHx(x = 0–4) on graphene.
functions (DNP) and all electron basis sets were used for all atoms. The Site Eads (eV) d (Å)
smearing value was chosen as 0.005 and the spin unrestricted was se-
lected. CH4 Top −0.33 3.358a
CH3 Top −0.46 1.585a
The transition states structures and the reaction pathways were lo-
CH2 Bridge −2.94 1.515b
cated by using the complete LST/QST method [33]. First, the linear CH Bridge −2.20 1.482b
synchronous transit (LST) maximization was conducted followed by an C Bridge −1.36 1.308b
energy minimization in directions conjugate to the reaction pathway. H Top −1.52 1.128a
Then, the TS approximation was used to perform quadratic synchro- a
nous transit (QST) maximization. After that, another conjugate gradient For the distance from the C atom of CHx(x = 0–4) to the C atom of gra-
phene right under the CHx.
minimization was processed. Finally, a stationary point would be lo- b
For the distance from the C atom of CHx(x = 0–4) to the nearest C atom of
cated when the cycle was carried out. The convergence criterion for TS
calculations was set to 2.0 × 10−3 Ha/Å. The frequencies of the geo-
metry optimization and TS search were both calculated with the same
3. Results and discussion
method, and the TS confirmation was performed on each transition
state to ensure the validity of both reactants and products.
3.1. Calculation of CH4 molecule and graphene

2.2. Model At the very first beginning of this computational study, to ensure
that the calculation method of this study is precise and credible, it is
In this study, a periodic 5 × 5 graphene supercell containing 50 quite essential to figure out the optimized geometry structure of the
carbon atoms was constructed. The lattice parameters were 12.30 Å, CH4 molecule and graphene, respectively. The CeH bond length and
12.30 Å and 20.00 Å in the a, b and c directions, respectively, which ∠HeCeH angle of CH4 obtained from this calculation are r(C-
prevented interactions between periodic images. Three adsorption sites H) = 1.097 Å and θ(H-C-H) = 109.471°, which are in consistent with the

were considered for graphene in this work, namely, top of a carbon experimental data of 1.096 Å and 109.4°, respectively [34]. And the
atom (Top), the midpoint of a CeC bond (Bridge), and the center of a results indicate that the CeC bond length of graphene is measured to be
hexagonal carbon ring (Center), as indicated in Fig. 1. It is accepted that 1.42 Å, which is exactly the same as the experimental value of 1.42 Å
the adsorption energy can be a criterion to evaluate the adsorption for graphite and graphene. At the same time, the ∠CeCeC angle is
effect, which means that the adsorption effect would be better with the equal to 120° and the optimized graphene retains the planar form. As a
increase of the value of adsorption energy. The adsorption energy (Eads) consequence, the above results clearly confirm the credibility of this
can be defined using Eq. (1): calculation method.

Eads = Egraphene + CHx (x = 0–4)−(Egraphene + ECHx (x = 0–4) ) (1) 3.2. Adsorption of CHx(x = 0–4) and H on graphene

where Egraphene + CHx (x = 0–4) is the total energy of the optimized graphene Before investigating the mechanism of CH4 dissociation on gra-
system on which the CHx(x = 0–4) is adsorbed, and Egraphene and phene, it is supposed to work out the individual bonding nature of all
ECHx (x = 0–4) are the energies of the pristine graphene and the the related species adsorbed on graphene. Therefore, it is essential to
CHx(x = 0–4), respectively. The values of Eads are all supposed to be study all the different adsorption sites of the species to get the most
negative. Besides, the equilibrium distance (d) is defined as the distance stable configurations of the CHx(x = 0–4) and H adsorbed on graphene.
between the carbon atom of CHx(x = 0–4) and graphene plane (Top, Then, the steadiest configurations of the CHx/H(x = 0–3) co-adsorbed
Bridge or Center). on graphene can be obtained. After that, the dehydrogenation

K. Li et al. Applied Surface Science 459 (2018) 693–699

Fig. 2. Top and side views of the most stable configurations of CHx and H adsorbed on graphene.

mechanism of CH4 into C and H is studied in detail, of which each physisorption.

elementary reaction will be included. Adsorbed CH3. The adsorption energies of CH3 adsorbed on gra-
Adsorbed CH4. It is widely accepted that it is the adsorption site phene are −0.46 eV, 0.35 eV and −0.08 eV for the sites of top, bridge
rather than the molecular orientation of the methane molecule ad- and center, respectively. Among the three optimized structures, the
sorbed on graphene that determines the adsorption results. Thus, the most stable adsorption site is the top site with the distance between the
orientation that three H atoms of CH4 point towards the graphene is C atom of CH3 and the C atom of graphene of 1.587 Å. As indicated in
studied, and three typical adsorption sites for graphene plane are con- Fig. 2b, CH3 is adsorbed on the graphene with the C atom downwardly
sidered in this work, namely, Top, Bridge and Center. Besides, the while the axis of CH3 is perpendicular to the graphene. And the CeH
calculated adsorption energies and related structural parameters are bond length is 1.098 Å, which is greater than that of free CH3 (1.087 Å).
summarized in Table 1. From Table 1, it can be seen that the adsorption Adsorbed CH2. The calculated adsorption energies of CH2 adsorbed
energies of the top, bridge and center sites are −0.33 eV, −0.27 eV and at the three sites are given in Table 1 with the value of the bridge site of
−0.22 eV, respectively, which means that the adsorption of CH4 on the −2.94 eV, and the initial structure at the top site is optimized into a
top site is the most stable configuration. Apart from that, it also in- more stable form at the bridge site, which proves that the methylene
dicates that the adsorption of CH4 on graphene is a process of molecule (CH2) appears to be favorably adsorbed at the bridge site.

K. Li et al. Applied Surface Science 459 (2018) 693–699

Fig. 3. Top and side views of the optimized stable co-adsorbed configurations of CHx/H on graphene.

Table 2 leading to two CeC bonds with the same bond length of 1.523 Å. Si-
The co-adsorbed energies and stable adsorption sites of the CHx/H(x = 0–3) on milar to the model of CH adsorbed on the graphene, the triangle is also
graphene. perpendicular to the graphene plane.
Site Eco − ads (eV) Adsorbed H. The H atom adsorbed at bridge site is converted to the
top site after structure optimization, and from Fig. 2 it can be seen that
CH3/H Top/top −2.585 the adsorption energies of the top site and bridge site are both
CH2/H Bridge/top −4.109
−1.52 eV, which indicates that the top site is the most stable config-
CH/H Bridge/top −3.538
C/H Bridge/top −2.694
uration. As shown in Fig. 2f, the H atom is bonded to the C atom of
graphene with the bond being perpendicular to the plane, and the bond
length is 1.128 Å, which is shorter than that of the regular CeH bond
Table 3 (1.14 Å).
The energy of barrier, energy of reaction and imaginary frequency of each re- Based on the above results, it is concluded that CH4, CH3 and H
action. atom prefer to be adsorbed at the top site, and CH2, CH and C prefer to
be adsorbed at the bridge site. As presented in Table 1, the adsorption
Energy of Energy of reaction Imaginary frequency
barrier (eV) (eV) (cm−1) energies of the CHx(x = 0–4) adsorbed on the graphene increase at the
beginning but decrease later with the increase of the H atom number of
CH4 → CH3 + H 4.118 2.576 −150.2 CHx, and the absolute value of the adsorption energy is the biggest
CH3 → CH2 + H 3.132 2.515 −211.2 (−2.94 eV) when CH2 is adsorbed at the bridge site. It also shows that
CH2 → CH + H 3.490 3.492 −440.3
CH → C + H 2.952 2.781 −685.9
the adsorption of CH4 is a typical physisorption, and the other ad-
sorption models are chemical adsorption process.

From Fig. 2c, it is observed that the C atom of CH2 bonds to the nearest 3.3. The co-adsorption of CHx(x = 0–3) and H on graphene
two C atoms of the graphene with both the bond lengths of 1.513 Å, and
this C atom points towards the midway of the CeC bond right beneath To analyze the reaction mechanism of the sequential dissociation of
the CH2. The length of the CeH bond and the angle of the HeCeH of CH4 on graphene, it is necessary to establish the co-adsorbed config-
CH2 are 1.089 Å and 116.8°, respectively, but the values of the free CH2 urations of CHx(x = 0–3) and H on graphene. The co-adsorbed energy
are 1.12 Å and 101.5° accordingly, which suggests that CH2 is disturbed Eco − ads of this model can be defined using Eq. (2):
slightly after adsorption.
Eco − ads = Egraphene + CHx + H−(Egraphene + ECHx + EH ) (2)
Adsorbed CH. The top site is optimized into the bridge site, and the
adsorption energies of CH adsorbed at the top site and bridge site are where Egraphene + CHx + H is the total energy of the optimized graphene
both −2.20 eV, which implies that the bridge site is the most stable system on which the CHx and H are adsorbed, and Egraphene , ECHx and EH
configuration and there is strong interaction between CH and graphene. are the energies of the pristine graphene, the CHx and the H atom, re-
As shown in Fig. 2d, the C atom of CH is bonded to the nearest two C spectively.
atoms of graphene with both the CeC bond lengths of 1.47 Å. The tri- In all calculation, each co-adsorption model is simulated based on
angle made up with three C atoms is perpendicular to the graphene the adsorption energies of CHx and H during the dehydrogenation of
plane while the CeH bond points obliquely towards the plane with the CH4, and the CHx and H are separately placed at the adjacent and the
bond length of 1.09 Å, which is shorter than that of free CH (1.14 Å). most stable adsorption sites in the co-adsorption models. For example,
Adsorbed C. It is interesting that both the C atoms adsorbed at top the most stable adsorption sites for the CH3 and H adsorbed on the
site and center site are changed into the bridge site after optimization, graphene are both top site, so CH3 and H are both placed at the top site
and the adsorption energies for all the three sites are −1.36 eV, which in the initial co-adsorption model of CH3/H. As indicated in Fig. 3a, the
obviously manifests that the bridge site is the most stable structure. In distance of the HeCH3 is 3.099 Å, of which the co-adsorbed energy is
Fig. 2e, it shows that the C atom interacts with the graphene plane −2.585 eV. Afterwards, Fig. 3b gives the co-adsorbed model of CH2/H

K. Li et al. Applied Surface Science 459 (2018) 693–699

Fig. 4. Top and side view of the TS structures for CH4 dehydrogenation on graphene.

the most stable configuration of CH4 adsorbed on graphene is the IS,

then the FS is the most stable co-adsorption model of CH3/H on gra-
phene. In order to verify the structure of the transition state (TS), the
frequency analyses of TS for CH4 dissociation have been carried out. As
listed in Table 3, it is obvious that each TS has only one imaginary
frequency, which means that TS confirmation is performed on each TS
structure to ensure the accuracy of the reactants and products. Besides,
all the TS structures are shown in Fig. 4, and the energy of barrier and
energy of reaction for each step are listed in Table 3. The energy pro-
files of the dissociations from CH4 to C and C2H6 on graphene are shown
in Fig. 5.

3.4.1. CH4 → CH3 + H

The first TS1 configuration of CH4 dissociation is shown in Fig. 4a,
in which the CH3 is adsorbed at the top site of the graphene and the
breaking H atom is bonded to the nearest C atom of graphene with the
Fig. 5. The energy profiles of the dissociations from CH4 to C and C2H6 on CeH bond length of 1.158 Å. This dehydrogenation reaction requires
graphene. the system to overcome the energy barrier of 4.118 eV for further re-
action, which is an endothermic process with the reaction energy of
2.576 eV.
on graphene, in which the CH2 and H are located at the bridge site and
top site, individually, with the distance of the HeCH2 of 2.839 Å. And
the co-adsorption energy of this structure is −4.109 eV. Furthermore, 3.4.2. CH3 → CH2 + H
the stable co-adsorption configuration of CH/H is shown in Fig. 3c, in For the dissociation of CH3 on graphene, the structure where CH3 is
which the adsorption sites of the CH and H are the bridge site and top adsorbed at the top site is considered as the IS, and the most stable co-
site, respectively, and the co-adsorbed energy of this structure is adsorption model of CH2/H is regarded as the FS. For TS2 in Fig. 4b, the
−3.538 eV with the distance of the CeCH of 2.376 Å. Finally, the stable CH2 fragment is slightly tilted and the H atom moves to the top site with
co-adsorbed configuration of the C/H is presented in Fig. 3d, in which the distance between H and CH2 elongated to 1.795 Å. After TS, the CH2
the C and H are adsorbed at the bridge site and top site, respectively, is located at the bridge site of the graphene with strong interactions.
and the co-adsorbed energy of this configuration is −2.694 eV with the The energy barrier and reaction energy of this elementary reaction are
distance between the C and H of 2.710 Å. As a result, all the co-ad- 3.132 eV and 2.515 eV, respectively, indicating an endothermic reac-
sorbed energies and stable adsorption sites of the CHx/H(x = 0–3) on tion.
graphene are listed in Table 2, and the corresponding configurations are
presented in Fig. 3. 3.4.3. CH2 → CH + H
For the third dehydrogenation, the most favorable adsorption con-
figuration with CH2 occupying the bridge site is regarded as IS, and the
3.4. Mechanism for CH4 dissociation most stable co-adsorption model of CH/H is regarded as FS. For TS3 in
Fig. 4c, the distance between the dissociated H and CH is stretched from
After obtaining the most stable co-adsorption configurations of 1.089 Å to 2.083 Å, and a new CeH bond is formed with the length of
CHx/H(x = 0–3) species, which are CH3/H, CH2/H, CH/H and C/H, it is 1.214 Å. After TS, the CH2 is still located at the bridge site, while the H
convenient to investigate the mechanism of methane dissociation on atom moves to the top site with the CeH bond of 1.154 Å. Besides, as
graphene. In this study, the optimized stable CH4, CH3, CH2, and CH are indicated in Table 3, the dehydrogenation of CH2 to CH and H needs to
chosen to be the initial states (IS), and the corresponding final states overcome an energy barrier of 3.490 eV with the reaction energy of
(FS) are the CH3/H, CH2/H, CH/H and C/H, respectively. For example, 3.492 eV.

K. Li et al. Applied Surface Science 459 (2018) 693–699

Fig. 6. The IS, TS and FS of the formed C2H6 on graphene.

Table 4 calculation shows that the system needs to overcome the energy barrier
The comparison of the dissociation of CH3 and the synthesis of C2H6. of 1.812 eV, and the energy of reaction is −3.125 eV indicating an
Adsorption Adsorption Energy of Energy of
exothermic process.
energy of IS energy of FS barrier reaction By comparing these two reactions in Table 4, it can be seen that the
(eV) (eV) (eV) (eV) barrier energy of the first reaction is larger than that of the second one,
and more importantly, the first reaction is endothermic while the
CH3 → CH2 + H −0.762 −4.109 3.132 2.515
second reaction is exothermic. Therefore, when the methyl group is
CH3 + CH3 → C2H6 −1.823 −0.762 1.812 −3.125
produced by the dissociation of CH4, the next step of the reaction is
more likely to produce the ethane by combining two methyl group
3.4.4. CH → C + H rather than dissociating CH3 into CH2 and H.
In the case of the CH dissociation, the most favorable adsorption
configuration of CH on bridge site is chosen to be the IS, and the most 4. Conclusion
stable co-adsorption model of C/H is considered as the FS. During the
dissociation process, the C atom remains at the bridge site while the In summary, a systematic investigation of the adsorption and dis-
dissociated H atom moves to the top site resulting in the new CeH bond sociation of methane on graphene has been studied by DFT calculation.
with the length of 1.214 Å, as indicated in the TS4 of Fig. 4d. This step On the basis of the adsorption energy analyses, CH4, CH3 and H atom
requires conquering the energy barrier of 2.952 eV with the reaction prefer to be adsorbed at the top site, of which only CH4 is physically
energy of 2.781 eV. adsorbed, and CH2, CH and C are favorable of the bridge site. Based on
the TS calculation, it shows that the dissociation of CH4 into CH3 and H
3.5. Formation of C2H6 during the dissociation of CH4 (CH3 + CH3 → is a rate-determining step. Besides, by comparing the dissociation of
C2H6) CH3 into CH2 and H and the formation of C2H6 during the dissociation
of CH4, it is obvious that the CH3 groups are more likely to produce
As implicated in many literature, there are different kinds of species ethane.
detected during the fabrication of C/C composites, which includes C2H6
[35,36]. Besides, Becker et al. [13], reported that with the methyl ra- Acknowledgments
dical ethane can be formed. Consequently, it is necessary to investigate
the formation of C2H6 from the atomic level when the methyl groups The authors gratefully acknowledge the financial support of this
are produced by the dissociation of methane. study by National Natural Science Foundation of China under Grant No.
As discussed, the most stable adsorption site for CH3 on graphene is 51521061, the Fundamental Research Funds for the Central
the top site. As a result, when studying the most favorable co-adsorp- Universities (No. 3102014JCQ01030), the Research Fund of the State
tion configuration of two CH3 on graphene, each CH3 is still located at Key Laboratory of Solidification Processing (NWPU), China (Grant No.
the top site. And the calculation shows that when the distance between 136-QP-2015).
the two CH3 is 4.022 Å, this model is the most stable structure, which is
regarded as the IS with the co-adsorption energy of −1.823 eV. In the References
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