Applied Surface Science 343 (2015) 121–127

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Applied Surface Science

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

A first-principles study on gas sensing properties of graphene and

Pd-doped graphene
Ling Ma a,b , Jian-Min Zhang a,∗ , Ke-Wei Xu c , Vincent Ji d
a
College of Physics and Information Technology, Shaanxi Normal University, Xian 710062, Shaanxi, PR China
b
School of Physics and Electrical Information Engineering, Ningxia University, Yinchuan 750021, Ningxia, PR China
c
State Key Laboratory for Mechanical Behavior of Materials, Xian Jiaotong University, Xian 710049, Shaanxi, PR China
d
ICMMO/LEMHE, Université Paris-Sud 11, 91405 Orsay Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: Sensitivity of pristine graphene (PG) and Pd-doped graphene (Pd-G) toward a series of small gas molecules
Received 1 January 2015 (CO, NH3 , O2 and NO2 ) has been investigated by first-principles based on density functional theory (DFT).
Received in revised form 11 March 2015 The most stable adsorption configuration, adsorption energy, charge transfer, density of states and mag-
Accepted 13 March 2015
netic moment of these molecules on PG and Pd-G are thoroughly discussed. It is found that four gas
Available online 21 March 2015
molecules are weakly adsorbed on PG with low adsorption energy of 0.08–0.24 eV, and the electronic
properties of PG are only sensitive to the presence of O2 and NO2 molecules. In contrast, doping graphene
Keywords:
with Pd dopants significantly enhances the strength of interaction between adsorbed molecules and the
Gas sensitivity
Pd-doped graphene
modified substrate. The dramatically increased adsorption energy and charge transfer of these systems
Density functional theory are expected to induce significant changes in the electrical conductivity of the Pd-G sheet. The results
reveals that the sensitivity of graphene-based chemical gas sensors could be drastically improved by
introducing the Pd dopants, so Pd-G is more suitable for gas molecules detection compared with PG.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction CO, NO2 and NO on a graphene substrate using first-principles

Graphene, a one-atom-thick carbon honeycomb structure, has
attracted considerable attention due to its intriguing electric and
transport properties since its discovery in 2004 [1–6]. It is worth
mentioning that the electronic state of graphene near the Dirac
point shows linear energy dispersion and zero band gap [6]. This
unique electronic property makes graphene easily doped with elec-
trons or holes, for example, by the small polar molecules adsorbed
on graphene [7,8]. Thus, graphene has been proposed that such a
device may be used as a highly sensitive gas sensor [9]. The experi-
ments by Schedin et al. [7] have shown that the H2 O, NH3 , CO, and
NO2 molecules can be detected using graphene devices at rather
low concentrations of molecules by monitoring the variation of
carrier densities upon adsorption of these molecules on graphene,
and even the ultimate sensitivity of an individual molecule was
suggested for NO2 . Meanwhile, theoretical studies were performed
to fully exploit the possibilities of graphene sensors. For instance,
Leenaerts et al. [10,11] investigated the adsorption of H2 O, NH3 ,
∗ Corresponding author. Tel.: +86 29 85308456.
E-mail address: jmzhang@snnu.edu.cn (J.-M. Zhang).
calculations and presented two different types of charge transfer
mechanisms.
However, because of the inert nature of the ␲-electron conju-
gation formed by carbon atoms of graphene, only weak adsorption
was found in most cases when these molecules interact with
pristine graphene nanomaterials [12]. To overcome these limi-
tations, some other recent theoretical studies [13–16] proposed
that heteroatom doping on graphene might significantly enhance
the chemical reactivity of the system and improve the adsorption
of molecules onto graphene. Zhou et al. [13] performed first-
principles to study the adsorption of small gas molecules (O2 , CO,
NO2 , and NH3 ) on the graphene embedded with various transi-
tion metal (TM) atoms and found that the embedded TM atoms
in general can significantly increase the interactions between gas
molecules and graphene. Ti and Au may be the best choices among
all TM atoms for applications of graphene-based catalysis. Dai et al.
proposed most of doped graphene are sensitive to O2 moleclule [14]
and Al-doped graphene can be sensitive to most of common gases
[15]. Shao et al. [16] investigated the adsorption of SO2 molecule on
graphene and heteroatom-doped graphene samples and suggested
that the Cr- and Mn-doped graphene can be more suitable for the
detection of SO2 gas. However, very few reports have been found
about gas adsorption on Pd-doped graphene.

http://dx.doi.org/10.1016/j.apsusc.2015.03.068
0169-4332/© 2015 Elsevier B.V. All rights reserved.
122 L. Ma et al. / Applied Surface Science 343 (2015) 121–127
Among TM atoms, Pd is five times cheaper than Pt and elec-
trochemically more stable than other TM atoms like Fe, Co and Ni
[17], and Pd adsorbed carbon nano-materials also can be utilized as
a promising catalyst [18]. For instance, single-walled carbon nano-
tubes (SWCNT) and graphene coated with Pd nanoparticles have
high sensitivity to H2 [19,20]. In this paper, we present detailed
studies of the adsorption of a series of small gas molecules (CO, NH3 ,
O2 and NO2 ) on pristine graphene (PG) and Pd-doped graphene
(Pd-G) by first-principles calculations based on density functional
theory (DFT). These gas molecules we chose are all of great practi-
cal interest for industrial, environmental and medical applications.
Meanwhile, NO2 and NH3 represent typical electron acceptors and
donors, which may undergo charge transfer with graphene. The
purpose of this work is to gain fundamental insights into the influ-
ence of different adsorbed molecules on the electronic properties
of pristine and Pd-doped graphene, and how these effects could be
used to design more sensitive gas sensing devices.
2. Calculation methods and models
All calculations in this paper are performed with the first-
principles method based on DFT by using the Vienna ab initio
simulation package (VASP) with a projector augmented wave
(PAW) method [21–24]. The electron exchange-correlation inter-
actions are expressed with a generalized gradient approximation
(GGA) in the form of the Perdew–Burke–Ernzerhof (PBE) [25] func-
tional. In fact, GGA and local densities approximation (LDA) with
DFT calculations are unable to describe correctly van der Waals
(vdW) interactions resulting from dynamical correlations between
fluctuating charge distributions. Concretely speaking, GGA under-
estimates the relatively weak binding energies, whereas LDA
overestimates them [26,27]. A pragmatic method to work around
this problem has been given by the DFT-D approach, in which
a dispersive force correction based on interatomic potentials of
the C6 ·R−6 form is added to a standard DFT exchange-correlation
functional—allowing for a facile energy decomposition to vdW and
electronic parts. Representatives of DFT-D methods are the imple-
mentations of Ortmann, Grimme and Tkatchenko [28]. Grimme’s
DFT-D2 method is adopted in our work. In the method, the vdW
interactions are described via a simple pair-wise force field, which
is optimized for several popular DFT functionals [29]. The cut-
off energy for the plane-wave basis expansion is chosen to be
400 eV. During relaxations, the positions of all atoms are allowed
to fully relax until the force on each atom is less than 0.02 eV/Å
between two ionic steps and the convergence of the electronic self-
consistent energy is less than 10−4 eV. Integration over the Brillouin
zone is performed by using the Gamma-centered Monkhorst-Pack
scheme [30] with (4 × 4 × 1) k-points, together with a Gaussian
smearing broadening of 0.2 eV.
The total system is modeled using a 4 × 4 graphene supercell
with a vacuum spacing of 15 Å, including graphene with a C atom
substituted for a Pd atom and a single gas molecule adsorbed on
it. The reason for using this structure is to remove the interac-
tions of the nearest Pd atoms and gas molecules themselves. For
the adsorption of the molecules CO and NH3 , we use non-spin-
polarized calculations, while for O2 and NO2 , we use spin-polarized
ones. Different molecular orientations and adsorption sites are cal-
culated to find the most stable adsorption configuration that has the
lowest total energy and the highest adsorption energy. The adsorp-
tion energy, Ea , is defined as: Ea = E(G) + E(S) − E(G/S), where E(G),
E(S) and E(G/S) denote the energies of the isolate gas molecule, the
substrate (PG or Pd-G) and the combined gas molecule-substrate
system, respectively.
As a preliminary test, we have optimized the atomic geometry
of 4 × 4 graphene supercell using the aforementioned calculation
Fig. 1. The optimized geometry of Pd-G: (a) Top view and (b) side view. The green
and blue balls represent the carbon and palladium atoms, respectively.
method and parameters. After full relaxation, the lattice constant
is 2.46 Å, which is in good agreement with the experimental value.
Then, the atomic geometries of the small gas molecules (CO, NH3 ,
O2 and NO2 ) also have been optimized. Our calculations present
the bond lengths 1.144 Å, 1.024 Å, 1.234 Å and 1.214 Å for CO, NH3 ,
O2 and NO2 molecules, respectively. The bond angles of NH3 and
NO2 , denoted by  (H N H) and  (O N O), are calculated to
be 106.5◦ and 133.8◦ . O2 and NO2 are paramagnetic molecules that
have a magnetic moment by 2 ␮B and 1 ␮B. The results are very
close to those obtained in previous experimental and theoretical
studies [31–36].
3. Results and discussions
At first, the geometry of Pd-G is investigated as a substrate for
gas adsorption. When one Pd atom substitutes for one C atom in
graphene sheet, the optimized structure of graphene sheet is sig-
nificantly distorted, as shown in Fig. 1. The Pd atom introduces the
deformation of the six-membered ring (6MR) near the doping site
to relieve stress, resulting in the Pd atom protruding out of the
graphene sheet. The height, h, defined as the distance between the
Pd atom and the graphene sheet, is calculated to be 1.61 Å; The
Pd C length, lPd C , defined as the distance between the Pd atom
and its nearest C atom in graphene sheet, is 1.96 Å, the result is
very close to that obtained in previous study performed by Wanno
et al. (lPd C = 1.965 Å) [37]. The local curvature from this geometric
property enhances the local reactivity [36], and it is expected that
this can play an important role in gas adsorption. We also calculated
the binding energy of Pd atom in graphene sheet (Eb ). Eb is calcu-
lated as: Eb = E(G) + E(Pd) − E(Pd-G), where E(G), E(Pd) and E(Pd-G)
are the total energies of the graphene with one C vacancy, the iso-
late Pd atom and the Pd-doped graphene (Pd-G), respectively. It is
worth mentioning that the Pd’s binding energy of the Pd-G has a
significantly high value of 5.37 eV, showing the Pd-doping is ener-
getically possible. This value is also larger than the cohesive energy
of Pd (3.89 eV [38]) also shows the Pd atoms can be well dispersed in
the graphene sheet and effectively prevent Pd clustering. Therefore,
the Pd-G has great geometric stability.
Next we focus on the adsorption of gas molecules on Pd-G
together with that on PG for comparison. In order to obtain the most
stable adsorption configuration, the gas molecule is initially placed
at different position above the PG or Pd-G with various orientations.
After relaxation, the optimized configurations obtained from the
different initial states are compared to search for the most favor-
able one. The most stable configurations of CO, NH3 , O2 and NO2
molecules on PG and Pd-G are summarized in Fig. 2. More detailed
information from the eight optimized configurations, including
adsorption energy Ea , adsorption length l (defined as the length of
nearest atoms between graphene and small gas molecules), bond
 L. Ma et al. / Applied Surface Science 343 (2015) 121–127 123

Fig. 2. Optimized configurations for CO, NH3 , O2 and NO2 adsorbed on PG ((a)–(d)) and Pd-G ((e)–(h)). Note that various configurations have been considered and we only
present here the most stable configurations. The green, red, orange and blue balls represent the carbon, oxygen, nitrogen and palladium atoms, respectively.

Fig. 3. The isosurfaces of the charge density differences for CO (a), NH3 (b), O2 (c) and NO2 (d) adsorbed on Pd-G. The red and green colors represent the charge accumulation
and depletion, respectively, and the value for the isosurface is 0.003 e/Å3 . It is found that NH3 molecule acts as a donor, and while CO, O2 and NO2 act as acceptor.

length of small gas molecules after adsorption d, charge transfer remains the value as in the gas phase (1.144 Å) and the charge trans-
from substrate to gas molecules Q and magnetic moment of the ferred from PG to CO is only 0.015 e. So the CO undergoes weak
total system (M), are listed in Table 1. The charge transfer from physisorption on PG due to vdW interaction between the graphene
substrate to gas molecules (Q) is calculated by Bader analysis and CO. The results are close to those obtained in previous study
of charge distributions, by which one can obtain the amount of performed by Zhang et al. [40]. On Pd-G, the most stable configura-
electron belonging to each atom and thus a summation over a few tion is changed dramatically after CO adsorption (see Fig. 2(e)). The
atoms belonging to an adsorbed molecule. Following the previous C O bond is tilted toward the plane of Pd-G and the C atom closes to
work by Lee et al. [39], in order to clearly present the charge trans- the Pd atom, with greatly increased adsorption energy (1.05 eV) and
fer induced by gas adsorption, we calculate the isosurfaces of the significantly decreased adsorption length (2.03 Å), indicating that
charge density differences for CO, NH3 , O2 and NO2 adsorbed on the interaction of CO with Pd-G is much stronger than that with
Pd-G, as shown in Fig. 3. These values are obtained by subtracting PG and this interaction involves chemisorption. Q = 0.155 e in CO
charge densities of Pd-G and the adsorbed gas molecules from those adsorbed on Pd-G is one order larger than 0.015 e in CO adsorbed
of the total system, namely,  = total − Pd-G − gas . In following on PG, further suggesting that the local electronic structure of Pd-G
sections, we discuss in detail the adsorption of gas molecules in the is clearly changed and CO is sensitive to this structure.
order CO, NH3 , O2 and NO2 . To figure out the effect of the Pd impurity on the reactivity of
graphene toward CO molecule, the total density of states (DOS) of
3.1. CO adsorption Pd-G with and without CO molecule adsorption were calculated
together with that of PG for comparison, as shown in Fig. 4(a)
On PG, the most stable adsorption site for CO is located above the and (b). Compared with PG, the contribution from CO is localized
center of the 6MR and nearly parallel to the graphene surface along between −10 and −5 eV in the valence bands and around 2.5 eV
the axis of two opposite C atoms of the 6MR (see Fig. 2(a)). Form in the conduction bands for PG with CO molecule, which far away
the Table 1, the adsorption energy of this system is calculated to be from the Fermi level. However, its DOS near the Fermi level have
0.08 eV and the adsorption length is 3.22 Å, the C O bond length no distinct change and the evident conductance change of this sys-
tem is barely observable (see Fig. 4(a)), so PG is not sensitive for the
Table 1
presence of CO molecule. In contrast, the DOS of CO adsorbed Pd-G
CO, NH3 , O2 and NO2 adsorbed on PG and Pd-G: adsorption energy (Ea ), adsorption has slightly changed around the Fermi level (see Fig. 4(b)). The lev-
length (l) (defined as the length of nearest atoms between graphene and small gas els are slightly shifted upward and become partially occupied due
molecules), bond length of small gas molecules after adsorption (d), charge transfer to some electrons from Pd-G transfer to CO, and there is a weak
from the substrate to gas molecules (Q) and magnetic moment of the total system
hybridization between O-2p and C-2p orbitals of CO molecule and
(M).
Pd-4d orbitals near the Fermi level as shown in Fig. 4(c).
Configuration Ea (eV) l (Å) d (Å) Q (e) M (␮B ) In addition, it is found that the PG sheet is semimetal (see
CO on PG 0.08 3.22 1.144 0.015 0 Fig. 4(a)), while a band gap (Eg ) of 0.29 eV is opened after Pd doping.
CO on Pd-G 1.05 2.03 1.154 0.155 0 However, due to the Gaussian broadening applied to the DOS cal-
NH3 on PG 0.09 2.91 1.024 −0.009 0 culations, this small Eg is not visible in this figure (Fig. 4(b)) but
NH3 on Pd-G 1.09 2.26 1.026 −0.112 0
it can be clearly seen in the band structure as shown in Fig. 4(g).
O2 on PG 0.08 3.35 1.243 0.082 2.00
O2 on Pd-G 1.28 2.14 1.347 0.586 0.95 It is worth mentioning that the system of Pd-G with CO adsorp-
NO2 on PG 0.24 3.18 1.228 0.204 0.79 tion is experiencing a relatively small decrease in its Eg (0.16 eV).
NO2 on Pd-G 2.17 2.22 1.28 0.663 0 It is well known that Eg is a major factor determining the electrical
124 L. Ma et al. / Applied Surface Science 343 (2015) 121–127

16
G (a) G (d) (g)
CO-G NH3-G 2
12

DOS (arb.units)

Energy (eV)
Eg=0.29 eV
8 0

4
-2

0
16
Pd-G (b) Pd-G (e) (h)
CO-Pd-G NH3-Pd-G 2
12
DOS (arb.units)

Energy (eV)
8 0
Eg=0.16 eV

4
-2

0
4
Pd-4d (c) Pd-4d (f) (i)
O-2p H-1s
PDOS (arb.units)

C-2p N-2p

Energy (eV)
2
Eg=0.39 eV

0
-20 -15 -10 -5 0 5 -20 -15 -10 -5 0 5 M K M
Energy (eV) Energy (eV)

Fig. 4. The total density of states (DOS) of PG (a), Pd-G (b) with and without CO molecule adsorption. DOS of PG (d), Pd-G (e) with and without NH3 molecule adsorption.
The partial density of states (PDOS) projected on Pd-4d orbitals, O-2p orbitals and C-2p orbitals (on CO) for PG with CO molecule adsorption (c). PDOS projected on Pd-4d
orbitals, H-1s orbitals and N-2p orbitals for Pd-G with NH3 molecule adsorption (f). The band structures for Pd-G (g), CO absorbed on Pd-G (h), NH3 absorbed on Pd-G (i). A
Fermi level is set at zero energy and indicated by the green dashed line.

conductivity of a material and there is a classic relation between
them as follows [41]:
 −E 
g local electronic structure is changed. In order to prove it, we have
 ∝ exp , (1)
2kT
It is established that in a fixed temperature, although small
change in Eg , causes considerable changing in electric conductivity
of conducting material, because the conductivity is exponentially
correlated with negative value of Eg (where  is electric conduc-
tivity of semiconductor and k is the Boltzmann’s constant). Based
on these facts, it is expected that Pd-G could directly convert the
presence of CO to the electrical signal. Similar behaviors are also
presented in Al doped graphene toward HCN molecule performed
by Hadipour et al. [42]. Therefore, Pd-G can be expected to be a
suitable device for CO detection
3.2. NH3 adsorption
The most energetically favorable configurations for NH3 adsorp-
tion on PG and Pd-G are shown in Fig. 2(b) and (f), respectively.
For the PG, the three H atoms of NH3 molecule point towards the
graphene plane. The adsorption of NH3 on PG is physical interaction
with the adsorption energy of 0.09 eV and the adsorption length of
2.91 Å. Different from CO adsorbed on PG, there is only small charge
of 0.009 e transfer from NH3 to the substrate, and NH3 molecule acts
as a donor. Clearly, PG is not sensitive to NH3 molecule. This result
is consistent with early theoretical reports [40]. On Pd-G, NH3 is
attached to the Pd atom with the N atom pointing at the substrate,
which gives the expanded adsorption energy of 1.09 eV and the
shorten adsorption length of 2.26 Å in compare with NH3 adsorbed
to PG, suggesting that the interaction between NH3 and Pd-G is
chemisorption. The charge transferred from NH3 to Pd-G is 0.112 e,
which is higher than that of NH3 adsorbed to PG, indicating that the
also investigated the electronic structures of NH3 adsorbed on PG
and Pd-G. Similar to CO adsorption on PG, the DOS of NH3 adsorbed
to Pd-G near the Fermi lever have no distinct change in compare
with that of PG (see Fig. 4(d)). However, the DOS of NH3 adsorbed
Pd-G has altered near the Fermi level and the Eg increases to 0.39 eV
as show in Fig. 4 (i) (due to the same reason, it is not obvious in the
DOS), which can result in the electric conductivity change. Hence,
Pd-G can be used as NH3 sensors. Different form CO adsorption on
PG, the all levels is slightly moved towards lower energy after NH3
adsorption owing to the charge transferred from NH3 to Pd-G (see
Fig. 4(e)). Meanwhile, the hybridization between H-1s and N-2p
orbitals of NH3 molecule and Pd-4d orbitals near the Fermi level is
barely observed as shown in Fig. 4(f).
It should be noted that, the PBE method usually underesti-
mates the band gaps of the semiconductor materials, that is to say,
the band gaps obtained here may be lower than the actual val-
ues. Although underestimation of band gaps exists in the present
calculations, this does not influence the relative comparison. One
way to solve this problem is to evaluate the self-energy for the
quasiparticles using the many-body perturbation theory with the
Green’s function method within the so-called GW approximation
[43]. Another way is the Heyd–Scuseria–Ernzerhof (HSE) screened
hybrid density functional, which based on a screened Coulomb
potential for the nonlocal Hartree–Fock-type exchange interaction
[44,45]. The two methods have been successfully used in describing
a wide range of the materials.

8 10
O2-G
4
DOS (arb.units)
0 0
-4
-20 -15 -10 -5 0 5
Energy (eV)
Fig. 5. DOS of PG (a), Pd-G (b) with O2 molecule adsorption. PDOS projected on Pd-4d orbitals and O-2p orbitals for Pd-G with O2 molecule adsorption (c). A Fermi level is
set at zero energy and indicated by the green dashed line.
3.3. O2 adsorption
As shown in Fig. 2(c), O2 is located on the hollow site with the
O O bond perpendicular to the graphene surface for O2 adsorbed
on PG. The calculated adsorption energy value is 0.08 eV and the
adsorption length is 3.35 Å. The low adsorption energy and long
distance demonstrate a weak physical interaction. It is well known
that graphene is non-magnetic and O2 is paramagnetic molecules
that have a magnetic moment of 2 ␮B in our calculations. For the O2
adsorption on PG, there is no magnetic moment change of both the
O2 molecule and the substrate, namely, the total magnetic moment
of this system is still 2 ␮B and PG cannot influence the magnetism
of O2 molecule. To verify the effect of the O2 adsorption on the
graphene’s electronic property, the DOS of the system is presented
here as shown in Fig. 5(a). It is found that the adsorption of O2
has considerably modified the shape of the DOS. There is a DOS
peak for spin-down electrons appearing at the Fermi level, which
indicates that the system is metallic and a significant increase in
conductivity. Therefore, PG is sensitive to O2 molecule. On Pd-G,
O2 is adsorbed with O O bond lying nearly parallel to the sub-
strate, which has greatly increased adsorption energy of 1.28 eV
and the dramatic decreased adsorption length of 2.14 Å, suggest-
ing that the interaction of O2 with Pd-G is much stronger than that
with PG. The O O bond length stretches to 1.347 Å, slightly longer
than that before adsorption (1.234 Å). The charge transferred from
Pd-G to O2 is 0.586 e, which is much larger than that of PG with
O2 (0.082 e). Obviously, the local electronic structure of Pd-G is
remarkably changed due to the O2 adsorption. Besides, Pd-G is non-
magnetic in our calculations, which is consistent with early works
[46]. Upon adsorption of paramagnetic O2 molecule, the substrate
still remains non-magnetic state, while the magnetic moment of
O2 molecule is decreased from 2 ␮B (before adsorption) to 0.95 ␮B.
As shown in Fig. 6, the spin-polarization densities for the system
also prove it. There is no spin distribution in Pd-G substrate. That is
because the partial unpaired states in O2 molecule are occupied by
getting electrons from Pd-G. Different from Pd-G, it is found that the
directions and magnitudes of magnetic moments of Co or Fe doped
graphene have been changed after adsorptions of gas molecules
Fig. 6. The spin-polarization densities for the Pd-G with O2 molecule adsorption
((r) = ↑ (r) − ↓ (r)). The red (green) isosurfaces correspond to the predominant
spin-up (spin-down) electron density of +0.01 e/Å3 (−0.01 e/Å3 ).
L. Ma et al. / Applied Surface Science 343 (2015) 121–127 125
(a) O2-Pd-G (b) 2
Pd-4d (c)
O-2p
PDOS (arb.units)
5
DOS (arb.units)
0
-5
-10 -2
10 -20 -15 -10 -5 0 5 10 -15 -10 -5 0 5 10
Energy (eV) Energy (eV)
[47]. In order to further understand the electronic properties of the
system, DOS and PDOS of O2 on Pd-G are calculated (see Fig. 5(b)
and (c)). It is found that there is one DOS peak for both spin-up
and spin-down electrons appearing at the Fermi lever. Meanwhile,
the system has transformed from semiconductor to metal due to
O2 adsorption. It is noticed that the DOS peak of spin-up electrons
at the Fermi lever is caused by Pd-4d orbitals, while the peak of
spin-down by Pd-4d and O-2p orbitals. Moreover, the hybridiza-
tion of Pd-4d and O-2p orbitals also happens here according to
the PDOS analysis, shown in Fig. 5(c). These changes in the DOS,
especially in the region near the Fermi level, are expected to bring
about obvious changes in the corresponding electronic properties,
which is beneficial for sensing applications. So it is concluded that
the Pd-G is more suitable for sensing application for O2 molecule
than PG.
3.4. NO2 adsorption
On PG, it is found that NO2 molecule is bonded to PG with both
O atoms down producing the cycloaddition configuration in agree-
ment with Ref. [13] (see Fig. 2(d)). The adsorption of NO2 on PG is
physical interaction with a moderate adsorption energy of 0.24 eV
and the adsorption length of 3.18 Å. It should be noted that there
is the large charge transferred from PG to NO2 , about 0.204 e, indi-
cating obviously change occurring in the local electronic structure.
To confirm this point, the DOS of PG with NO2 molecule adsorp-
tion is plotted in Fig. 7(a). It can be clearly seen that a DOS peak
of spin-down electrons appears at the Fermi level and the system
exhibits metallic and magnetic property. Similar to O2 , NO2 is also
paramagnetic molecule. Its magnetic moment is decreased from
1 ␮B (before adsorption) to 0.79 ␮B for the same reason with O2 on
Pd-G, and the substrate is still non-magnetic. Based on these facts,
PG is sensitive for the presence of NO2 molecule. For NO2 adsorbed
on Pd-G, the NO2 is bonded to the Pd atom with both O atoms
down producing the cycloaddition configuration (see Fig. 2(h)).
The adsorption energy and the adsorption length are 2.17 eV and
2.22 Å, respectively, which indicates that NO2 is chemisorbed on
Pd-G. A dramatic charge transfer (0.663 e) from the substrate to
NO2 is observed. It is interesting that the magnetic moment of NO2
is diminished after NO2 adsorption, suggesting that the unpaired
states in NO2 molecule are fully occupied by getting electrons from
Pd-G. Next, Fig. 7(b) and (c) shows the DOS and PDOS of Pd-G
with NO2 adsorption. Compared with PG, it is obvious that the
DOS of Pd-G has significantly changed and the related levels are
shifted upward inferring that NO2 acts an acceptor. There is a high
peak occurring in the Fermi level, which is mainly caused by Pd-4d
orbitals and a weak hybridization of Pd-4d orbitals and O-2p and
N-2p orbitals of NO2 happens here (Fig. 5(c)). Hence, Pd-G can be
used to detect this molecule.
126 L. Ma et al. / Applied Surface Science 343 (2015) 121–127
10
NO2-G (a)
5 N-2p
DOS (arb.units)
DOS (arb.units)
0 2
-5
-10
-20 -15 -10 -5 0 5 10
Energy (eV)
Fig. 7. DOS of pristine graphene (a), Pd-doped graphene (b) with NO2 molecule adsorption. PDOS projected on Pd-4d orbitals, O-2p orbitals and N-2p orbitals for Pd-doped
graphene with NO2 molecule adsorption (c). A Fermi level is set at zero energy and indicated by the green dashed line.
4. Conclusions
The first-principles calculations based on DFT are performed in
order to study the adsorption of a series of small gas molecules (CO,
NH3 , O2 and NO2 ) on PG and Pd-G in terms of energetic, geomet-
ric, electronic and magnetic properties. Our results indicate that
the adsorption of four gas molecules on PG undergo a weak phys-
ical interaction with low adsorption energy of 0.08–0.24 eV, and
the electronic properties of PG are only sensitive to the presence
of O2 and NO2 molecules. Compared with PG, Pd-G shows higher
adsorption energy with CO, NH3 , O2 and NO2 molecules and has a
higher chemical reactivity towards these gas molecules owing to
the impurity of Pd atom. The strong interaction between adsorbed
molecules and the modified substrate induces dramatic changes to
the electrical conductivity of Pd-G. Therefore, Pd-G is more effective
than PG in detecting gas molecules because of its high sensitivity.
Acknowledgements
The authors would like to acknowledge the State Key Develop-
ment for Basic Research of China (Grant No. 2010CB631002) and the
National Natural Science Foundation of China (Grant No. 51071098)
for providing financial support for this research.
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