Applied Surface Science 311 (2014) 377383

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Chemical functionalization of graphene by carbene cycloaddition:

A density functional theory study
Wenyan Zan
College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China

a r t i c l e

i n f o

Article history:
Received 19 March 2014
Received in revised form 6 May 2014
Accepted 12 May 2014
Available online 19 May 2014
Keywords:
DFT
Graphene
Functionalization
Carbene groups

a b s t r a c t
In this work, we have systematically studied the structural, energetic and electronic properties of
graphene functionalized with carbene groups by using density functional theory. Introducing a low
concentration of CCl2 group in graphene was studied in detail by DFT, and closed cyclopropane-like
three-membered ring structure was formed, meanwhile, the potential candidate carbene groups CR2
(R = H, F, CH3 , CN, NO2 , OCH3 , CCH, C6 H5 ) were added to graphene sheet, and CR2 (R = H, NO2 , CH3 ) groups
were expected to be good reactive species to covalently modify graphene. The graphene functionalization
with carbene groups above can open graphenes band gap. More CCl2 molecules were added to graphene,
and different concentrations of CCl2 group can tune graphenes band gap. In addition, the addition of CCl2
group to graphene edges was investigated, and the stronger binding energy was found. Multiple CCl2
molecules preferred to be bound with the same edge of graphene nanoribbon. This work provides an
insight into the detailed molecular mechanism of graphene functionalization with carbene groups.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Graphene is regarded as a very promising material for
applications in solid-state sensors, energy storage, fuel cells,
nanoelectronics, and spintronics owing to its excellent properties [18] including unique geometric structure, high electron
mobility, high-integer quantum Hall effect at room temperature,
spin transport, high elasticity, high mechanical strength, tunable
band gap, tunable optical properties, and high thermal conductivity. Nevertheless, some problems remain in poor solubility,
intrinsic zero band gap energy and low reactivity of pristine
graphene, which has put a brake on the rapid development of
graphene. In this regard, graphene functionalization can adjust
graphenes original properties to further broaden the application
elds.
The functionalization of carbon materials with carbene groups
has been extensively studied. Haddon et al. [9] as pioneers have
achieved the addition of CCl2 molecule to single-wall carbon
nanotubes (SWCNTs) in 1998, then this cycloaddition was widely
applied for the functionalization of CNTs [1013]. It has been
demonstrated that SWCNTs reacting with a carbene molecule can
form the usual three-membered ring or get the opening of the

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E-mail address: zanwy11@lzu.edu.cn
http://dx.doi.org/10.1016/j.apsusc.2014.05.071
0169-4332/ 2014 Elsevier B.V. All rights reserved.

sidewalls [1416] by DFT calculations in some reported theoretical investigations. Reactive intermediates of radicals, nitrenes,
carbenes, and arynes through free radical addition, CH insertion,
or cycloaddition reactions were also used to covalently modify
graphene [1721]. More recently diazirines were employed to functionalize reduced graphene oxide by Workentin and co-workers
[19]. Subsequently, Pumera and co-workers [20] have successfully attained the graft of dichlorocarbene on chemically reduced
graphene based on a conventional method. However, there is still
lack of fundamental understanding about graphene functionalization with carbene molecules at atomic scales, especially the
mechanism of graphene functionalization with carbene groups.
Hence, we believe that the process of graphene functionalization
with carbene molecules is important and valuable to be intensively
studied by theoretical methods.
Herein, according to the results from Pumera et al. [20], atomicscale investigations of graphene functionalization with carbene
groups were systematically reported by using DFT methods to
uncover the following unclear questions: (1) How is the reaction
process of graphene functionalization with a low concentration of
CCl2 group in atomic scale carried out? (2) How are the potential
candidate carbenes CR2 (R = H, F, CN, NO2 0 , NO2 90 , CH3 , OCH3 , CCH,
C6 H5 ) separately combined with graphene? (3) How does the band
gap of graphene with the different coverages of dichlorocarbene
group change? (4) How about the functionalization of graphene
nanoribbon with dichlorocarbene group?

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W. Zan / Applied Surface Science 311 (2014) 377383

Fig. 1. The most stable congurations of the functionalized graphene sheet by CR2 (R = Cl (a), H (b), CH3 (c), NO2 0 (d), NO2 90 (e),C6 H5 (f), CN (g)).

2. Models and methods

We carried out the all-electron ab initio density functional
theory (DFT) calculations using the generalized-gradient approximation (GGA) with the PerdewBurkeErnzerhof (PBE) function
[22]. The double numerical basis set with the polarization function (the DNP basis set) was implemented in the DMol3 package
[23]. The GGA/PBE method has also been successfully employed
to study graphene systems in previous theoretical studies [2427].
The convergence criterion of optimal geometry for energy, force,

and displacement were 1.0 105 Ha, 0.002 Ha/ and 0.005 A,
respectively. The periodic boundary condition was used with
a tetragonal supercell of 17.22 17.22 30 A 3 (seven periodic
lengths of graphene layer in both x and y directions) which is
large enough to completely remove the image interactions. The
impact of various (n n 1) k-point meshes on the binding energy
for a CH2 -functionalized graphene was examined. The binding
energies could converge after 3 3 1 k-point meshes, so the
Brillouin zone was sampled by 3 3 1 special k-points using
the MonkhorstPaeck scheme [28] in the meantime, a 15 15 1
k-points was used for calculating electronic properties. The binding energy (Eb ) of the functionalization of graphene is dened
as Eb = [Etotal (graphenecarbene) (Etotal (graphene) + nEtotal (carbene))]/n, where Etotal is total energy of the system in bracket,
and n stands for the number of added carbene groups. In such a
denition, a negative binding energy means an exothermic addition reaction on graphene. The adsorption energies is dened
using the equation: Eads = Eadsorbate/M (Eadsorbate + EM ), where Eads
is the adsorption energy of the adsorbate on the graphene plane,
Eadsorbate/M is the energy of the adsorbate/M adsorption system,
and Eadsorbate and EM are the energies of the free adsorbate and
the clean sheet, respectively. By this denition, stable adsorption will have negative adsorption energy. The band gaps (Eg )
between the highest-occupied molecular orbitals (HOMOs) and the
lowest-unoccupied molecular orbitals (LUMOs) at the  point, band
structures and density of states (DOS) were calculated to predict the
electronic properties.
Transition state searches were performed by the linear/quadratic synchronous transit (LST/QST) method in Dmol3
[29,30]. In this method, an LST/optimization calculation was

executed rst, and followed by QST/maximization calculation,

and then conjugate gradient (CG) minimization was performed.
The cycle was repeated until a stationary saddle point (transition
state) was located. This method has been widely used to search for
transition state of reaction on graphene surface [3134].

3. Results and discussion

3.1. Graphene functionalization with a low concentration of
dichlorocarbene and other potential candidate carbene groups
A systematic analysis of graphene functionalization by a low
concentration of dichlorocarbene was performed. First, the positions of a single dichlorocarbene above the graphene were located
at different initial states including the hollow site, top and bridge
sites of C atoms, then, after full relaxation, the most stable conguration was presented in Fig. 1a. We found that a single CCl2
was attached to the graphene through [1 + 2] cycloaddition, and the
The
bond lengths of the newly formed C C bonds were 1.543 A.
small binding energy value (Eb = 0.399 eV) corresponded to the
small 0.054 electrons transfer from graphene to CCl2 by the Mulliken population analysis, revealing that the interaction of graphene
and CCl2 was relatively weak, whereas there were two C atoms
from the graphene were pulled outward the graphenes plane, so
the natural properties of graphene have been changed.
To gain more sight into the process of the graphene functionalization with the single CCl2 , we studied the detailed reaction
process of adding a single dichlorocarbene to the graphene, as it
followed the concerted mechanism demonstrated by Houk et al.
[35]. The reaction prole of the graphene functionalization with a
single CCl2 was shown in Fig. 2a. Herein, for the physisorption of a
CCl2 on graphene sheet, two adsorption sites including atop C atom
and atop the bridge site of C C bond were considered to nd the
most favorable adsorption structure, and through our calculation,
the top site of C atom was more preferred (Fig. 2a (reactant)). In
this conguration, the CCl2 group paralleled the graphene, and
respectively.
the distances of C1 C2 , C1 C3 were 3.156, 3.531 A,
The bond lengths and angles of CCl2 group and graphene barely
changed before and after adsorption, indicating that the adsorption

W. Zan / Applied Surface Science 311 (2014) 377383

379

Table 1
Bond lengths, binding energies and charge transfer for carbenes (R = H, CN, NO2 0 ,
NO2 90 , CH3 , C6 H5 ) attached to the graphene sheet.
R

H
CN
NO2 0
NO2 90
CH3
C6 H5

dc

c /

1.512
1.611
1.507
1.567
1.552
1.554

1.512
1.611
1.507
1.569
1.549
1.554

1.579
1.513
1.581
1.533
1.565
1.558

Eb /eV

q/e

1.988
0.095
1.496
0.910
1.163
0.276

0.137
0.204
0.159
0.230
0.146
0.104

a, b: The bond lengths of the newly formed C C bond. c: The bond lengths of the
C C bonds on the graphene sheet where carbenes are attached.

Fig. 2. (a) Calculated structures of the initial state (reactant), transition state (TS),
and nal state (product) for the functionalization of the graphene with the rst CCl2
group. (b) The functionalization of the graphene with the second CCl2 group.

of the single CCl2 molecule on graphene sheet was relatively weak

(Eads = 0.462 eV). The charge transfer between CCl2 group and
graphene sheet was further investigated by calculating Mulliken
charge populations, as it was found that just 0.034 electrons were
transferred from graphene to CCl2 group, which was coincident
with the weak interaction. For the optimized structure of the
transition state shown in Fig. 2a (TS), the C2 atom slightly elevated
from graphene plane and trended toward sp3 hybridization.

Meanwhile the C1 C2 bond was being formed (C1 C2 = 1.852 A),

The
and the C2 C3 bond distance was elongated to 1.470 A.
Mulliken population analysis showed that 0.054 electrons were
transferred from graphene to CCl2 . Fig. 2a (product) exhibited the
optimized structure of the product with C1 , C2 , and C3 forming a
C1 C3 : 1.543 A).
The C3 ,
closed triangular shape (C1 C2 : 1.543 A,
C2 atoms have become sp3 hybridization, which was consistent
with the trend predicted by Jing Lu [15]. The distance from C2 to
C3 was 1.560 A (single bonded C C species), and C C bonds aside
The product was slightly less stable than the initial
rose to 1.478 A.

adsorption state by 0.063 eV. Apparently, this cycloaddition reaction is much more likely to happen for so low energy barrier
(0.568 eV).
The future work in the experimental study for tuning the
graphenes band gap and improving the solubility of graphene
[20] was attaching a series of carbenes (CR2 , R = H, F, CH3 , CN,
NO2 , OCH3 , CCH, C6 H5 ) to graphene, thus, the additions of CR2
(R = H, F, CN, NO2 0 ; NO2 90 , CH3 , OCH3 , CCH, C6 H5 ) to graphene
were investigated, and C(NO2 )2 has two denitive extreme isomers: C(NO2 0 ) representing that the two NO2 groups are parallel
to each other; C(NO2 90 ) meaning that both NO2 groups are rotated
by 90 . These most stable optimized structures were displayed in
Fig. 1 with the bond lengths, binding energies, and charge transfer summarized in Table 1. We found that the additions of CR2
(R = F, OCH3 , CCH) on the graphene sheet were unable to form stable
complexes. Besides that, the behaviors of the remaining carbene
groups were similar to that of CCl2 group with formation of the
closed three-membered ring products, and the bond lengths of the
in the meantime,
three-membered ring were between 1.5 and 1.6 A,
some C atoms of graphene were also pulled out of the graphene
surface. As indicated in Table 1, the released heat followed the
order: CH2 > C(NO2 0 )2 > C(CH3 )2 > C(NO2 90 )2 > C(C6 H5 )2 > C(CN)2 . It
is likely that electron-acceptor substituent groups on the C atom
of carbenes decreased the activity of carbenes. However, C(C6 H5 )2
did not have the feature, and the lower binding energy of C(C6 H5 )2
was possibly related to the relatively strong steric hindrance effects.
The most released heat was 1.988 eV from the addition of CH2 to
graphene, which was less than that of SWCNTs, indicating that
graphene was less reactive [13]. Meanwhile, Mulliken charge populations showed that electrons were transferred from graphene to
carbene groups for CR2 (R = NO2 , CN) with electron-withdrawing
nature, while CR2 (R = H, CH3 , C6 H5 ) did the reverse due to electrondonating feature. In conclusion, CR2 (R = H, NO2 , CH3 ) were ready
for graphene functionalization.
One of the most important purposes of graphene functionalization is to modify graphenes electronic properties. The band
structures for original graphene and graphene functionalized with a
CCl2 molecule were plotted in Fig. 3. The Fermi level was set at 0 eV.
The projected density of states (PDOSs) for CCl2 and graphene sheet
were shown in Fig. 4 after graphene functionalization with a single
CCl2 . We found that pristine graphene was semimetallic, which was
accordant with the known results. Graphene functionalization with
a CCl2 molecule gave rise to an opening of the conduction band edge
(CBE) and valence band edge (VBE) of pristine graphene above the
Fermi energy, and there existed a band gap with 0.245 eV (Fig. 3).
It is worth noting that the DFT method usually underestimates the
band gap of semiconductors due to the self-interaction error [36],
however, the trend is credible [3739]. As displayed in Fig. 4, the
CCl2 molecule mainly hybridized with the p orbital of graphene
sheet between 10 and 0 eV, and CCl2 hybridized with the s orbital
of the graphene sheet from 15 to 10 eV. We further calculated
the electronic band structure of graphene with the additions of

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W. Zan / Applied Surface Science 311 (2014) 377383

Fig. 3. Electronic band structure of a graphene sheet (a) before and (b) after the addition of a single CCl2 group. Red dashed lines denote the Fermi level. K represents the 
point. (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)

Fig. 4. The projected density of states (PDOSs) of (a) CCl2 group and (b) the graphene
sheet after the graphene functionalized by a single CCl2 group.

CR2 (R = H; CN; NO2 0 ; NO2 90 ; CH3 , C6 H5 ). These above-mentioned

carbene groups had the very similar behaviors with the dichlorocarbene group, and the band gap of graphene was also opened and
became about 0.2 eV.
3.2. Graphene functionalization with a high concentration of
dichlorocarbene
The high coverage of CCl2 group on graphene sheet was further studied. First, the second CCl2 group was added to graphene
functionalized by a single dichlorocarbene, and we investigated the
particular reaction process, then more CCl2 molecules were bound
with graphene sheet until reaching eight CCl2 molecules, and more
than eight CCl2 molecules can not be bound with graphene due to
the large steric repulsion among these CCl2 groups. Fig. 2b showed

the reaction prole of graphene functionalization with a second

CCl2 , and the most stable congurations of functionalized graphene
with multiple CCl2 molecules were shown in Fig. 5.
A systematic investigation was carried out in order to determine the cycloaddition site of the second CCl2 group. These C C
double bond positions near or away from the rst CCl2 group on
graphene were studied, and the same or the other side of the rst
CCl2 group were also considered. After all the initial congurations
were optimized, the most favorable structure of the second CCl2
group on graphene not only located on meta-position of the rst
CCl2 group, but the other side (Fig. 2b (reactant)). Why did the
second CCl2 group prefer to locate on meta-position of the rst
CCl2 group? This fact can be explained by calculating projected
density of states (PDOSs) near the Fermi level of the C C bonds
at the meta-site and para-site of the rst CCl2 group, C C bond
away from the rst CCl2 group, and the rst CCl2 group (Fig. 6).
Obviously, the C C bonds at the meta-position had the sharper
peak near the Fermi level than other sites, indicating that metaposition was a more favorable site for the cycloaddition reaction
of dichlorocarbene. Meanwhile, the second CCl2 group located at
the other side site of the rst CCl2 group, which avoided the strong
repulsion. The adsorption behavior of the second CCl2 was similar
to the rst CCl2 , and the most stable conguration was also atop C
atom of graphene. However, the adsorption sites of the second CCl2
group was farther away from the graphene plane than that of the
rst CCl2 due to the damaged conjugated structure for graphene,
repectively.
as the distances of C4 C5 , C4 C6 were 3.601, 3.365 A,
The adsorption energy was 0.082 eV with small amount of charge
transfer (0.018e) from graphene to CCl2 . Subsequently, the optimized conguration of the transition state was shown in Fig. 2b
(TS) through the transition state search. Sp3 hybridization was also

formed to the C5 atom, and the distance from C4 to C5 was 1.938 A.

At the end, closed three-membered ring structure was formed by
C4 C6 : 1.569 A;
C5 C6 : 1.513 A)

C4 , C5 , and C6 (C4 C5 : 1.530 A;

(Fig. 2b (product)). At this point, two three-membered rings distributing over graphene sheet up and down owned the same bond
lengths and bond angles. The activation energy was calculated to

W. Zan / Applied Surface Science 311 (2014) 377383

381

Fig. 5. The stable congurations from 1 to 8 CCl2 molecules on the graphene.

Fig. 6. The projected density of states (PDOSs) of (a) CCl2 group, (b) the meta -site
carboncarbon double bond, (c) the para -site carboncarbon double bond (d) other
site carboncarbon double. Red dashed lines denote the Fermi level. (For interpretation of the references to color in this gure legend, the reader is referred to the
web version of this article.)

be 0.418 eV, indicating that the addition of the second CCl2 group
to graphene was much more easily conducted, and the product was
much more stable than the initial complex by 0.737 eV.
One by one, multiple CCl2 molecules were attached onto
graphene sheet until reaching eight CCl2 molecules. CCl2 molecules
evenly spaced around the graphene plane up and down to eliminate mutual interference, and no matter how many CCl2 molecules
were added to graphene, closed three-member ring structures
were formed in all congurations. The average binding energies
of these congurations for graphene functionalized by multiple CCl2 molecules (from 1 to 8) were 0.399, 0.590, 0.556,
0.625, 0.564, 0.562, 0.520, 0.490 eV, respectively, illustrating the thermal stability of graphene functionalization with

Fig. 7. The Eg change as the functionalization of the graphene with the number of
CCl2 groups from one to eight.

different concentrations of dichlorocarbene. In the meantime, there

was 0.080.09 electrons transfer from graphene to dichlorocarbene. Obviously, pristine graphene can be functionalized by a high
coverage of dichlorocarbene.
What we want to know is the change for electronic properties
of graphene functionalized by multiple CCl2 molecules. The changing trend of functionalized graphenes band gap as functions of the
number of CCl2 group from 1 to 8 was summarized in Fig. 7. The
band gaps of graphene sheet with the addition of one, two, three,
four, ve, six, seven, eight CCl2 groups were 0.245, 0.190, 0.381,
0.218, 0.435, 0.027, 0.245, 0.571 eV, respectively, and the curve
reected apparently serrated rule (Fig. 7). It is clear that the different coverage of dichlorocarbene on graphene can regulate the
band gap of pristine graphene.

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W. Zan / Applied Surface Science 311 (2014) 377383

Fig. 8. The stable congurations from 2 to 5 CCl2 molecules on the edges of the AGNR.

3.3. Graphene nanoribbon functionalization with dichlorocarbene

The edge regions of graphene play an important role. Thus, we
studied the addition of dichlorocarbene to the graphene nanoribbon (GNR). The GNR with zigzag edge (ZGNR) possessed higher
activity than armchair edge (AGNR) due to edge effect [40]. So the
GNR with armchair edge was elected, and the edges of AGNR were
saturated with hydrogen atoms. For the AGNR functionalization
with CCl2 group, the formation of closed three-membered ring was
analogous to the case with graphene, however, the binding energy
of the AGNR functionalized by a single CCl2 was more than six times
than that of graphene sheet, and obviously, the addition reaction
on the edges of AGNR was much easier than that of graphene. We
studied that multiple CCl2 molecules were attached to the edges of
AGNR. The second CCl2 group added to the AGNR preferred to be far
away from the rst CCl2 group due to intermolecular repulsion, and
all the CCl2 molecules tended to be added to the same edge of the
as a result of the activation of the AGNR edges (Fig. 8). The average
binding energies of the congurations for the AGNR functionalized
with multiple CCl2 molecules (from 2 to 5) were as follow: 2.076;
1.988; 1.947; 1.920 eV, respectively, and the strong binding
energy showed that the edges of AGNR were easy to be covered by
dichlorocarbene. The electronic properties of the AGNR functionalized with multiple CCl2 molecules were investigated. The AGNR
used in this paper was a wide band-gap semiconductor (1.197 eV),
which was consistent with the previous reports. The band gaps
of the AGNR with the addition of one, two, three, four, ve CCl2
molecules were 1.225, 1.116, 1.007, 0.898, 0.844 eV, respectively,
therefore, the introduction of CCl2 would not signicantly affect the
electronic properties of the AGNR.
4. Conclusions
We have studied the structural, energetic and electronic properties of graphene functionalized with carbene groups by using
density functional theory. A low concentration of dichlorocarbene attached to graphene was successfully attained and formed
closed three-membered ring structure, and the cycloadditions
of CR2 (R = H, F, CH3 , CN, NO2 , OCH3 , CCH, C6 H5 ) to graphene
were also studied. We found that CR2 (R = H, NO2 , CH3 ) were
expected to be good reactive species for the covalent modication
of graphene, moreover, owing to the introduction of these carbenes,
the graphene sheet was activated with its band gap opened. Adding
more CCl2 molecules to graphene sheet was energetically favorable, and the band gap of graphene can be tuned by introducing
different concentrations of CCl2 group. Additionally, the cycloaddition of dichlorocarbene to graphene nanoribbon was investigated,
and the more released heat during the process of graphene

nanoribbon functionalization than surface functionalization of

graphene indicated the higher activity of graphene edges. When
more CCl2 molecules were brought in graphene nanoribbon, it was
testied that these CCl2 groups preferred to locate on the same edge
of GNR, however, no matter how many CCl2 molecules were introduced in graphene nanoribbon, there was no signicant change in
band gap of graphene nanoribbon.

Acknowledgement
We are grateful to Huanxiang Liu and Xiaojun Yao from the
Lanzhou University for their valuable suggestions for improving
the paper.

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