Surface Science 612 (2013) 63–68

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Surface Science
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A theoretical study of CH4 dissociation on NiPd(111) surface

Kai Li a, Zhongjun Zhou a, b, Ying Wang a,⁎, Zhijian Wu a,⁎
a
State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, PR China
b
State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun 130023, PR China

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

Article history: The CH4 dissociation on the NiPd(111) surface is studied by using the density functional theory (DFT). The pos-
Received 4 January 2013 sible adsorption sites are proposed and the favorite adsorption site(s) are determined. The potential energy
Accepted 20 February 2013 curve for CH4 dissociation is presented. Compared with pure Ni(111) and Pd(111) surfaces, the dissociation of
Available online 27 February 2013
CH4 on NiPd(111) surface is more favored, especially on the Ni reaction center of NiPd(111) surface. The intro-
duction of Pd improves the Ni catalytic ability for CH4 dissociation. A synergistic effect exists between Ni and Pd
Keywords:
NiPd(111)
that results in an improved catalytic performance for CH4 disassociation over that of either parent metal. Bime-
CH4 dissociation tallic NiPd is predicted to be a good catalyst for CH4 dissociation, in good agreement with experiment.
Reaction barrier © 2013 Elsevier B.V. All rights reserved.

1. Introduction
The methane dissociation is the key to transform the resources of nat-
ural gas into useful products like hydrogen. However, the high stability of
methane makes it hard to dissociate at room temperature. Thus, catalytic
CH4 dissociation to produce hydrogen has attracted increasing attention
in recent years [1–9]. Because of the good catalytic activity and low cost,
Ni-based catalysts have become one of the most attractive catalysts in
CH4 dissociation. However, carbon deposition is a severe problem for
Ni-based catalysts and usually deactivates the catalysts [10–17]. Thus,
improving the activity of Ni-based catalysts and suppressing coke forma-
tion are challenging technological problems.
In order to improve the stability and activity of Ni-based catalysts, a bi-
metallic catalyst is often used, instead of pure Ni. Many Ni-based bimetal-
lic catalysts have been proposed by experiments, such as Ni–Cu, Ni–Co,
Ni–Pt, Ni–Au, Ni–Sn and Ni–Pd etc [18–41]. Among them, Ni–Au and
Ni–Sn bimetallic catalysts show a suppressed coke formation, but at the
cost of losing a catalytic activity [18,19]. Ni–Pt bimetallic catalyst with
the lowest Pt/Ni ratio (Pt0.3Ni10) exhibited a higher catalytic activity and
stability for CH4 dissociation than monometallic Ni [20,21]. In addition,
Ni–Pd bimetallic catalyst has received much attention for CH4 dissociation
because of the high activity and stability [22–27]. Takenaka et al. investi-
gated the CH4 dissociation over M–Ni/SiO2 (M = Cu, Rh, Pd, Ir, Pt) and
found that Pd–Ni catalysts had the highest yields of hydrogen with a
mole ratio of Pd / (Ni + Pd) = 0.5 [22,23]. Steinhauer et al. investigated
the catalytic activity of bimetallic Ni–Pd on different supports and found
that they had a better performance than single metal Ni or Pd-catalysts
for CH4 dissociation [24]. The superior catalytic performance of Pd pro-
moted Ni catalysts came from the synergistic effect between Ni and Pd
[25].
⁎ Corresponding authors. Tel.: +86 43185262801.
E-mail addresses: ywang_2012@ciac.jl.cn (Y. Wang), zjwu@ciac.jl.cn (Z. Wu).
On the theoretical side, there were also several studies available
by using the density functional theory (DFT). This included the CH4
dissociation over a Ni-based bimetallic (111) surface such as Ni–Au
[18,42,43], Ni–Co [44], Ni–Cu [45], Ni–Sn [19], or Ni–M surface
(M = Cu, Ru, Rh, Pd, Ag, Pt, and Au) [46], etc. The results indicated
that the introduction of Au and Sn to Ni made bimetallic surface less
active for CH4 dissociation and weakened C adsorption [18,19,43].
The relative high energy barriers and the low C binding energy
explained the experimentally observed coke resistance. To our
knowledge, theoretical study of CH4 dissociation over Ni–Pd surface
is still rare. Recently, the physical origin of the synergistic effect
over Ni–M surface (M = Cu, Ru, Rh, Pd, Ag, Pt, and Au) with Ni/
M = 3 was conducted [46]. Although the electronic structure and ad-
sorption properties had been investigated, the detailed reaction
mechanism of CH4 dissociation over NiPd was not provided. In this
work, we present a study on the possible reaction mechanism for
CH4 dissociation on NiPd(111) surface by using the density functional
theory (DFT). The Pd/Ni = 1 is selected based on the previous exper-
iment, because at this ratio, the hydrogen yield is the highest [23]. The
adsorption geometries, energies of CHx (x = 0–4) on NiPd(111) sur-
face and activation energies for the four elementary steps involved in
CH4 dissociation are investigated. For comparison, CH4 dissociation
on elemental Pd(111) and Ni(111) surfaces is also given.
2. Computational details
2.1. Method
The calculations were performed using Vienna ab-initio simula-
tion package (VASP) [47–50]. The interactions between valence elec-
trons and ion cores were treated by Blöchl's all-electron-like
projector augmented wave (PAW) method [51,52]. The exchange-
correlation functional was the generalized gradient approximation

0039-6028/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.susc.2013.02.012
64 K. Li et al. / Surface Science 612 (2013) 63–68
with the Perdew–Burke–Ernzerhof, known as GGA-PBE [53]. The
wave functions at each k-point were expanded with a plane wave
basis set with a kinetic cutoff energy up to 400 eV and electronic occu-
pancies were determined according to a Fermi scheme with an energy
smearing of 0.1 eV. Brillouin zone integration was approximated by a
sum over selected special k-points using the Monkhorst–Pack method
[54] and they are set to 3 × 3 × 1. Geometries were optimized until
the energy was converged to 1.0 × 10−6 eV/atom and the force con-
verged to 0.01 eV/Å. Because of the existence of magnetic atom, spin
polarization was considered in all calculations.
The transition state (TS) structures and the reaction pathway were
computed using the climbing image nudged elastic band (CI-NEB)
method [55]. The minimum energy path (MEP) was optimized
using a force-based conjugate-gradient method [50] until the maxi-
mum force is less than 0.01 eV/Å. In addition, TS was verified by
only one imaginary frequency.
2.2. Model
The NiPd alloy with Ni/Pd = 1 showed a remarkable performance
in CH4 dissociation and reforming [22–24]. The formation of the Ni–Pd
alloys was observed to include (111) and (200) surfaces by the XRD
pattern [26]. Thus, we choose the ground state of Ni (face-centered-
cubic lattice) [56,57] and replace half of the Ni atoms by Pd atoms to
simulate the 1:1 Ni–Pd alloy. The calculations show that the lattice con-
stants of alloy are a = 3.841 and c = 3.618 Å, different from the lattice
constants of Ni bulk (3.518 Å) and Pd bulk (3.920 Å). Since experimen-
tally, NiPd(111) and NiPd(200) surfaces are observed [26], in order to
determine which surface is more stable, the surface energy (Esurf) is in-
troduced which is defined as the energy of the slab related to its bulk
reference [58]:
E −nEbulk
Esurf ¼ slab
2A
where Eslab is the total energy of the surface slab, Ebulk is the total energy
of the bulk NiPd, A is the surface area with a factor of 2 due to each slab
containing two surfaces, and n is the number of NiPd formula units in
the slab. The small Esurf means that the surface is more stable [58].
Thus, the calculated Esurf values of 0.045 eV for (111) and 0.103 eV for
(200) indicate that NiPd(111) is more stable than (200). This is the rea-
son why we study NiPd(111) surface in this work.
The surface is obtained by cutting NiPd (fcc) bulk along (111) di-
rection, the thickness of surface slab is chosen to be a three-layer slab
which is proved to be a reasonable model and widely employed in
previous literatures [43–45]. In our calculations, the atoms in the
Fig. 1. Top view (a) and side view (b) of the possible adsorption sites on NiPd(111) surface.
bottom are fixed in their bulk positions, and those in the top and sec-
ond layers are allowed to relax. A vacuum layer as large as 12 Å is
used along the c direction normal to the surface to avoid periodic in-
teractions. In order to reduce the interaction between adsorbates on
the surface, a (2 × 2) supercell is used to model the coverage of a 1/4
monolayer.
The chemisorption energy, Eads, is defined as follows
ΔEads ¼ Eadsorbates=slab −ðEslab þ Eadsorbates Þ
where Eadsorbates/slab is the total energy of adsorbates on (111) surface,
Eslab is the total energy of the bare slab of the surface, and Eadsorbates is
the total energy of free adsorbates. The first two terms are calculated
with the same parameters. The third term is calculated by setting the
isolate adsorbate in a box of 12 Å × 12 Å × 12 Å. The negative ΔEads
indicates exothermic chemisorption, positive value suggests endo-
thermic chemisorptions, while values closer to zero (slightly negative
or slightly positive), are representative of weak physisorption.
3. Results and discussion
3.1. CHx adsorption on NiPd(111)
There exist nine possible adsorption sites on the NiPd(111) surface
(Fig. 1), they are, two different Top sites (TNi and TPd), Hexagonal
Close Packed sites (HCPNi and HCPPd), and Face Center Cubic sites
(FCCNi and FCCPd), as well as three different Bridge sites (BNi–Pd, BNi–Ni
and BPd–Pd). Here, we have investigated all the possible adsorption con-
figurations and energies of CHx (x = 0–4) and H on NiPd(111) surface
(see Fig. S1 in the supporting information).
3.1.1. CH4 adsorption on NiPd(111)
According to previous studies, CH4 adsorption is reported to be a
physisorption process on pure metal surfaces with an extremely
small adsorption energy [42–45]. Similarly, our results show that
the introduction of Pd also does not increase CH4 adsorption energy
significantly. The adsorption energy is calculated to be − 0.02 eV,
close to the values on pure Ni(111) (− 0.02) and Pd(111) (− 0.03)
surfaces, respectively.
3.1.2. CH3 and CH2 adsorption on NiPd(111)
From the adsorption energies of CH3 and CH2 on NiPd(111) (Fig. S1,
CH3(a) to CH3(h) and CH2(a) to CH2(g)), we find that CH3 and CH2 pre-
fer to occupy the hollow site with two Ni atoms, that is, FCCPd site as
shown in Fig. 2b and c. For CH3, all three H atoms point outward, with-
out interaction between H and Ni/Pd. For the adsorbed CH2, it is seen
 K. Li et al. / Surface Science 612 (2013) 63–68 65

that the energy is lowered when one H atom is bonded to the Ni atom,
which is favorable for the following dissociation of C–H. In the
favorite CH3 and CH2 adsorption configurations (Fig. 2b and c), C\Ni
bond lengths (2.115 Å in CH3, 1.859 and 1.980 Å in CH2) are shorter
than the C\Pd bond lengths (2.330 Å in CH3, 2.072 Å in CH2). This
might be an indication that the interaction between C and Ni is stronger
than that between C and Pd.
3.1.3. CH and H adsorption on NiPd(111)
CH prefers to locate at the hollow sites HCPPd and FCCPd, whose ad-
sorption energies are −6.27 eV and −6.24 eV, respectively, slightly
higher than −6.35 eV on the pure Ni(111) surface at the same level
of theory (Fig. S1, CH(a) to CH(d)). This indicates that CH on NiPd
alloy is less stable than on pure Ni surface. Similar situation is observed
in the previous studies on NiCo(111) and NiCu(111) [44,45].
Similar to CH adsorption configurations, H also prefers to adsorb at
hollow sites with four possible configurations (Fig. S1, H(a) to H(d)).
The calculated adsorption energies (around − 2.7 eV) are much
smaller than those for CH (around − 6.0 eV). In addition, the adsorp-
tion energies of the four H-adsorption configurations are very close
and the diffusion barrier of H on NiPd(111) is only 0.15 eV,
suggesting that the migration of H on the surface is relatively easy.
3.1.4. C adsorption on NiPd(111)
Different from the configurations on Ni(111) and Pd(111) sur-
faces, there are only three stable geometries for C adsorption on
NiPd(111) (Fig. S1, C(a) to C(c)). The initial structures FCCPd and
HCPPd are all converged to the most stable fourfold site (denoted as
FF in Fig. 2e). It is clear that when C is adsorbed on FF, the NiPd
(111) surface deforms severely. In this adsorption configuration,
compared to the isolated NiPd(111), the bond of Ni\Pd is shortened
from 2.674 to 2.648 Å, while Ni\Ni and Pd\Pd bonds are elongated
by 14.1% (from 2.723 to 3.106 Å) and 1.0% (from 2.723 to 2.749 Å),
respectively. The surface distortion is consistent with the experiment
observation by Takenaka et al. [22,23].

Fig. 2. The most stable adsorption geometries and selected parameters of CHx (x = 0–4) and H on NiPd(111) (only the top two layers of the NiPd slab are displayed in the top view,
and the top layer in the side view). The gray balls denote C atoms and the white balls denote H atoms. The top H–Ni indicates one of the H atoms pointing to the Ni atom.
66 K. Li et al. / Surface Science 612 (2013) 63–68

3.2. CH4 dissociation on NiPd(111)
In order to investigate the mechanism of CH4 dissociation on the
NiPd (111) surface, we choose the most stable geometry as the initial
state and co-adsorbed CHx − 1 + H species with the lowest Eads are
set as the final configurations in the minimum energy path. Each
step is divided into two possible pathways: one is with Ni as the
catalytic reaction center and the other is with Pd as the catalytic reac-
tion center.
3.2.1. CH4 → CH3 + H
As mentioned above, CH4 on NiPd(111) is a physical adsorption
process, and all configurations have almost the same adsorption ener-
gy. Therefore, we select the CH4 adsorption on the top of Ni or Pd con-
figurations as the initial state. As FCCPd is the most stable site for CH3
adsorption, while H adsorption has nearly the same stability for the
studied sites, the configurations of CH3 adsorbed at FCCPd and H locat-
ed at FCCPd are chosen as the final state in the first step of CH4 disso-
ciation on NiPd(111). Two transition states on two different reaction
centers are given in Fig. 3 (TS1 and TS1′, with the latter indicating Pd
as a reaction center). In the two configurations, the CH3 fragment is
adsorbed at the top site and the breaking H atom is located at the
nearest hollow site. The breaking C\H bond increases by 45.7%
(from 1.097 to 1.598 Å in TS1) or 48.3% (from 1.097 to1.627 Å in
TS1′) compared to the C\H bond length in isolated CH4, and the
forming Ni\H bond is elongated by 22.7% (from 1.723 to 2.114 Å in
TS1) or 27.3% (from 1.723 to 2.194 Å in TS1′) with respect to the
bond length of H adsorbed on FCCPd site. The elongation of the formed
bond is smaller than that of the breaking bond, indicating that the
two TSs are product-like. This means that the both reaction channels
proceed via a “late” transition state. This character in the TSs is consis-
tent with the calculated result that CH4 decomposition to CH3 and H is
an endothermic process with the reaction energies of 0.30 and
0.48 eV for the Ni and Pd reaction centers, respectively, in agreement
with Hammond's postulate [59]. It is worth to note that the reaction
energy with the Ni reaction center is less endothermic by 0.18 eV
compared to that of the Pd reaction center. In addition, the energy
barrier height of the reaction with the Ni reaction center (0.84 eV,

Fig. 3. The transition state structures for CHx (x = 1–4) dissociation on NiPd(111)(only the top two layers of the NiPd slab are displayed in the top view, and the top layer in the side
view). (a–d) for TS with the Ni reaction center and (e–g) for TS′ with the Pd reaction center. The C–H (rupture) indicates the breaking C\H bond. The vimag indicates the imaginary
frequency.
 K. Li et al. / Surface Science 612 (2013) 63–68
Fig. 4) is lower than that of the Pd reaction center (1.01 eV). This sug-
gests that taking Ni as the reaction center is favored both thermody-
namically and kinetically.
3.2.2. CH3 → CH2 + H
CH3 at the FCCPd site is the initial structure for CH3 dissociation,
while both of the CH2 and H co-adsorbed at FCCPd site are the final
states for the reaction with the Ni center. For the Pd reaction center,
the configuration of CH2 at FCCPd site and H at HCPPd site is set as
the final state. The two TS structures for CH3 dissociation on the
NiPd(111) surface are shown in Fig. 3b and f. In Fig. 3b. The carbon-
containing fragment CH2 is located at the FCCPd site and the detached
H atom is positioned at the adjacent hollow site with dC–H = 1.620 Å.
In Fig. 3f, the detached H is located on the top of the Pd atom with the
C–H distance of 1.834 Å. It is clear to see that the breaking C\H bond
length in the former case (Ni reaction center) is shorter than the lat-
ter (Pd reaction center) by around 0.2 Å, suggesting that CH3 dissoci-
ation is more difficult on the Pd reaction center than on the Ni
reaction center. The calculated CH3 dehydrogenation with the Ni re-
action center is endothermic only by 0.15 eV and the barrier height
is 0.64 eV (Fig. 4), while those for the reaction with Pd are 0.19 and
0.90 eV, respectively.
3.2.3. CH2 → CH + H
CH2 adsorbed at the FCCPd site (Fig. S1, CH2(a) and Fig. 2c) with
two Ni atoms is more stable than CH2 at the hollow site with two
Pd atoms (Fig. S1, CH2(d)–CH2(e)). In addition, in the former config-
uration, one of the H atoms bonded to Ni with the dNi–H = 1.732 Å.
Thus, the adsorbed H can be easily removed from CH2. Therefore,
we only consider the CH2 dehydrogenation with the Ni reaction cen-
ter. In TS3, as shown in Fig. 3c, the distance between C and the
cleaved H atom is 1.502 Å, which increases by 36.9% (from 1.097 to
1.502 Å) compared to the C\H bond length in isolated CH4, while
the Ni\H bond is elongated by 79.3% (from 1.723 to 3.090 Å). The ex-
tent of the elongation of the Ni\H bond is larger than that of the
breaking bond, indicating that the TS is reactant-like. Thus, the reac-
tion channel proceeds via an “early” transition state. This is consistent
to the early character of TS with an exothermic process (− 0.27 eV) in
Hammond's postulate [59]. It is noted that CH2 decomposition is the
only exothermic process in the whole CH4 dissociation processes on
NiPd(111) surface. Furthermore, the C–H dissociation barrier is the
lowest with an energy of 0.28 eV compared to other dissociation pro-
cesses (Fig. 4).
3.2.4. CH → C + H
For the Ni reaction center, CH at FCCPd is selected as the initial
structure, while for the Pd reaction center, CH at HCPPd is set as the
initial state since the adsorption for CH at HCPPd is slightly more sta-
ble than FCCPd by 0.03 eV (Fig. S2, CH(a)–CH(b)). The configuration of
C at FF and H at FCCPd sites is set as final state. The TS structures are
shown in Fig. 3d and g. In Fig. 3d, the breaking C\H bond is
1.562 Å, and its orientation is almost parallel to the surface. From
the calculated data, the deformation of NiPd(111) surface is obvious.
This is because compared with an isolated NiPd(111) (planar) sur-
face, the two Ni atoms bonded with C are enlarged by 11% (from
2.723 to 3.012 Å) on the xy plane, while the Pd and Ni bonded with
C rise about 0.187 and 0.023 Å above the surface (along z axis). The
energy barrier of CH dehydrogenation into C and H is 1.04 eV
(Fig. 4) and the reaction is endothermic by 0.32 eV, which is the
highest electronic barrier during the CH4 dissociation process. In
Fig. 3g, the C atom locates at the middle between two Ni atoms
with dC–Ni = 1.754 Å, and H moves toward the top of Pd with the
breaking C\H bond of 2.198 Å. However, the deformation of the sur-
face is not so large as that in the Ni reaction center. The activation en-
ergy for CH dissociation with the Pd center is 1.29 eV and the reaction
is endothermic by 0.35 eV. The higher barrier and more endothermic
67
on the Pd center also confirmed that the Ni reaction center is more
preferred. Thus, Ni atoms have a higher catalytic activity than Pd for
CHx (x = 1–4) dissociation.
3.3. Comparison with Ni(111) and Pd(111) surfaces
As discussed above, it is seen that Ni shows a higher catalytic activ-
ity than Pd on NiPd(111) surface, so the minimum energy path of the
reaction should be CH4 dissociation on NiPd(111) with the Ni center.
In order to show the performance of NiPd catalyst, we also investigat-
ed the mechanism of CH4 dissociation over pure Ni(111) and Pd(111)
surfaces by the same level of theory (possible configurations are
shown in Figs. S2–S4). The potential energy surface of CH4 dissociation
on Ni(111), Pd(111) and NiPd(111) surfaces is shown in Fig. 4. It is
seen that CHx (x = 1–4) dehydrogenation into CHx − 1 (x = 1–4)
and H on NiPd(111) is more favored both thermodynamically and ki-
netically than that on Ni(111) and Pd(111) surfaces.
A synergistic effect exists between Ni and Pd that results in the
improved catalytic performance of NiPd for CH4 dissociation over
that of either parent metal. This might be explained in the following.
First, the introduction of Pd changes the geometrical structure of
pure Ni. The lattice parameter increases from 3.518 Å in pure Ni to
3.841 Å for a and 3.618 Å for c in NiPd alloy. Second, it also makes
the surface charge redistributed. Our calculations indicate that with
the increase of x in CHx (x = 1, 2, 3), the average net charge of Ni
is positive and changes from 0.27, 0.28 to 0.30 |e|, while that of Pd
is negative from − 0.12, − 0.19 to − 0.22 |e|. The positive charge of
Ni and negative charge of Pd are in agreement with the small electro-
negativity of Ni (1.91) and large electronegativity of Pd (2.20). This
suggests that the Ni\Pd bond is polarized. Since the radicals of CHx
(x = 1–3) have redundant electrons, they prefer to be adsorbed to
the positive Ni. Thus, Ni becomes the reaction center.
Hanmmer and Nørskov pointed out that the d-band center of sim-
ilar transition metal correlates with the general catalytic activity and
the reactivity of the transition metal system increases as the d-band
center is shifted up [60,61]. Thus, to further explain why NiPd alloy
has a higher catalytic activity and Ni atom is the reaction center for
CHx dissociation, the d-band centers of the Ni(111), Pd(111) and
NiPd(111) surfaces are examined. Our calculated d-band centers of
pure Ni and Pd are − 1.47 eV and − 1.89 eV, respectively, while the
average value for NiPd is − 1.71 eV. Obviously, the average d-band
center of NiPd alloy surface is far away from a Fermi level compared
with Ni(111). However, the d-band center of Ni on NiPd(111) surface
is −1.14 eV, closer to a Fermi level than pure Ni, demonstrating that
CHx adsorbed on the sites with two Ni atoms is more stable than
on the other sites, and dissociations at the Ni reaction center are
Fig. 4. Potential energy curves for CH4 dissociation on Ni(111), Pd(111) and NiPd(111)
surfaces, respectively.
68 K. Li et al. / Surface Science 612 (2013) 63–68
preferred. Thus, we conclude that Ni–Pd synergistic effect enhances
Ni catalytic activity in alloy [46].
4. Conclusions
The mechanism of methane dissociation on NiPd(111) surface has
been investigated by using the density functional theory. Our results
show that CHx (x = 1–3) prefers to adsorb at the hollow sites with
two Ni atoms (FCCPd or HCPPd) and CHx (x = 1–4) dissociation on
the Ni reaction center is more favored than on the Pd reaction center.
The largest electronic energy barrier of CH4 dissociation is CH dissoci-
ation to atomic carbon and hydrogen on NiPd(111) surface. By com-
paring with pure Ni(111) and Pd(111) surfaces, we observed that
Ni–Pd alloy shows the highest catalytic activity. A synergistic effect
exists between Ni and Pd that results in an improved catalytic perfor-
mance for CH4 dissociation over that of either parent metal. We con-
clude that NiPd is a good catalyst to decompose CH4, consistent to the
experimental observation.
Acknowledgments
This work is financially supported by the National Natural Science
Foundation of China (grant nos: 20921002, 21273219, 21203174).
The authors are also thankful for the financial support from the De-
partment of Science and Technology of Sichuan Province. The compu-
tational time is supported by the Performance Computing Center of
Jilin University, China.
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://
dx.doi.org/10.1016/j.susc.2013.02.012.
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