Applied Surface Science 287 (2013) 97–107

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Applied Surface Science

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

DFT study on the structure of Ni/␣-Al2 O3 catalysts

Minhua Zhang, Jianyue Chen, Yingzhe Yu ∗ , Yongbo Zhang
Key Laboratory for Green Chemical Technology of the Ministry of Education, Tianjin University Research and Development Center for Petrochemical
Technology, Tianjin 300072, China

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

Article history: The stable adsorption sites of Ni atoms supported on the surface of ␣-Al2 O3 (0 0 0 1) were investigated
Received 21 April 2013 through the quantum chemistry computation based on density functional theory (DFT). It was found that
Received in revised form 21 August 2013 there exist only three kinds of stable adsorption sites on this surface, and the oxygen three-fold vacant site
Accepted 15 September 2013
is the preferential adsorption site for Ni atoms. The adsorption of Ni2 clusters on the␣-alumina surface
Available online 23 September 2013
consists of two configurations, i.e. horizontal and vertical adsorption. During the calculation, it was found
that the charge can transfer, when Ni clusters are adsorbed on the ␣-Al2 O3 surface, and the Ni clusters
Keywords:
can combine with ␣-Al2 O3 surface through local polarization. In this work, the loading of metal clusters
␣-Alumina
Ni2 cluster
on oxide surface and the concerned interaction between the both were studied based on the fundamental
Ni based catalyst theoretical analysis. The above information can provide some instructions for the design and synthesis
Density functional theory (DFT) of novel practical catalysts.
Structure © 2013 Published by Elsevier B.V.

1. Introduction
The alumina as catalyst and carrier material is widely applied
in the chemical industry because of its excellent catalytic activity,
thermal stability and mechanical strength [1]. The active transi-
tional metal components supported on alumina can be classified
into two main categories: the noble metals and the basic metals.
The noble metals, such as Ru, Rh, Pt, Ir, Pd and so on, are of
rather high catalytic activity. However, the limited resource and
high cost would restrict their industrial application [2,3]. Among
the basic transitional metals, the nickel based supported cata-
lyst has obtained great attention and showed extensive industrial
application prospect because of its higher activity, richer resource
and lowercost [4–6]. However, the deactivation of Ni based cat-
alysts, including carbon deposition, sintering and losing of active
components, has become the main problems in their industrial
applications [7]. To solve these problems, different kinds of car-
rier and promoter have been used to improve the catalytic activity
and stability. Therefore, the understanding on essential mecha-
nisms in practical industrial catalysts is often very complicated. It
can involve their geometric, crystallic and electronic performances.
Perhaps some active phases that are difficult to reduce will be
formed. Although the models of single crystal surface and metallic
surface can not completely express the real performances of sup-
ported catalysts, it might provide a convenient method to research
the supported model catalyst, thus has attracted many researchers,
∗ Corresponding author. Tel.: +86 22 27406119; fax: +86 22 27406119.
E-mail address: yzhyu@tju.edu.cn (Y. Yu).
who are engaged in studying the interaction between metals and
supports [8–12]. In fact, the interaction plays an important role for
the activity and stability of supported catalysts [13]. For instance,
the dissociation of CO on the Rh cluster/alumina catalyst will be
related with the cluster size to some extent [14]. Furthermore,
many reactions are carried out at rather high temperature, even
higher than 700 ◦ C, the outstanding thermal stability of catalysts
should also be required.
In this work, the␣-Al2 O3 supported nickel based catalysts will
be selected as the research object, the structure and properties of
nickel cluster on the ␣-Al2 O3 surface and the interaction between
them were revealed by the quantum chemistry computation based
on the DFT theory.
2. Computation module and method
2.1. Computation module
The support model applied in calculation is a periodic model.
The size of ␣-alumina unit cell is 8.24 × 9.52 × 16.85 Å. The (2 × 2)
super cell is adopted in this work in order to reduce the interaction
between neighboring atomic clusters on the support. The (0 0 0 1)
surface model of ␣-Al2 O3 is selected, which includes two layers of
Al atom, four layers of O atom and totally forty atoms. To avoid the
interplanar interaction caused by periodic boundary conditions, the
vacuum thickness is set to 13 Å.
It has been revealed that the (0 0 0 1) surface of ␣-Al2 O3 is the
most frequently exposed one and the oxygen atoms on ␣-Al2 O3
(0 0 0 1) surface is of hexagonal symmetric structure, and the out-
most surface layer has three different terminal faces. To satisfy the

0169-4332/$ – see front matter © 2013 Published by Elsevier B.V.

http://dx.doi.org/10.1016/j.apsusc.2013.09.082
98 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107
Fig. 1. Configurations of ␣-Al2 O3 (0 0 0 1) surface before and after structural opti-
mization.
three demands for the lowest repetition limit in the ␣-Al2 O3 atomic
layers i.e. charge neutrality, stoichiometric equilibrium and zero
dipole moment, the ␣-Al2 O3 (0 0 0 1) surface should be terminated
at the Al atomic monolayer [15]. The LEED analysis suggests that
the surface terminated at the Al monolayer is most stable [16]. In
this work, the surface energy of three terminal surfaces were cal-
culated, and the result indicated that the surface energy data for
the three surface models are (a) −1421.8300 Ha,(b) −1421.8760 Ha
and (c) −1421.6726 Ha, respectively, among which that of config-
uration (b) with the Alatoms terminated surface layer is obviously
lower than those of configurations (a) and (c). The result can reveal
that the structural energy of the oxygen atoms terminated surface
is the highest, which is consistent with the result calculated by
Yourdshahyan et al. [17].
To further study the structural performances of support surface,
the 2 × 2 surface of the ␣-Al2 O3 (0 0 0 1) surface is constructed.
The optimized surface configuration is shown as in Fig. 1. The Al
atoms on the first layer are relaxed, and situated almost on the
same plane as that of O atoms, which is consistent with the LEE
Dresult observed by Toof an and Watson et al. [18].
2.2. Calculation procedure and settings
The simulation of the system is carried out by the DFT
method, the periodic model is selected, and DSPP is set
to the nucleus processing mode. RPBE equation with gen-
eralized gradient approximation is applied in the calcula-
tion of electronic correlation, and the electronic polarization
effect is considered. During the simulation of interaction
between metallic cluster and support, the K point is set to
2 × 2 × 1.
The adsorption energy of the Ni cluster is defined as:
 
ads
ENi = − ENin /Al2 O3 − EAl2 O3 − ENin
n
where ENin /Al2 O3 is the total energy of ␣-Al2 O3 (0 0 0 1) surface
loaded with Ni cluster; EAl2 O3 is the surface energy of pure ␣-Al2 O3 ;
ENin is the energy of pure Ni cluster.
To investigate the supporting and aggregation of Ni cluster on
the ␣-Al2 O3 (0 0 0 1) surface, the aggregate energy of the Ni cluster
on ␣-Al2 O3 (0 0 0 1) surface can be defined as
 
ENin /Al2 O3 − EAl2 O3 − nENi
clu
ENi =−
n n
where the definitions of parameters ENin /Al2 O3 and EAl2 O3 are same
as those in formula (1), and ENi is the energy carried by Ni atom in
vacuum.
3. Calculation result and discussion
3.1. Stable adsorption of Ni1 on the surface of alumina
The ␣-Al2 O3 (0 0 0 1) surface is of the oxygen six-fold symmetric
structure as is shown in Fig. 2. The included angle between the Al
Fig. 2. The five adsorption sites on ␣-Al2 O3 (0 0 0 1) surface.
atom on outmost surface layer and three neighboring O atoms is
approximately 120◦ . The atoms on outmost surface layer are com-
posed of the O atoms with coordination number of 3 (3cO) and the
Al atom is bonded with three 3cO atoms, it can also interact with the
Al atom on fourth layer. The bond length between Ni and 3cO atoms
is approximately 1.953 Å, and that between Ni and the Al atom on
fourth layer is 2.592 Å (Fig. 3). Owing to the adsorption of Ni atom,
the bonded three 3cO atoms are lifted by about 0.1 Å, while their
relaxation on same plane is a little. The distance between three 3cO
atoms has changed only from 2.596 Å before adsorption to 2.598 Å
or 2.597 Å after adsorption. This fact suggests that the adsorption
of Ni atoms has little impact on alumina along the horizontal direc-
tion. Moreover, the Al atoms adjacent with the Ni atoms on surface
are pressed down by about 0.162 Å by the adsorption of Ni atom.
For the configuration of Ni1 –Al(3) ,the adsorption of Ni atom can
also lift the 3cO atoms by about 0.1 Å, whereas the adjacent Al
atoms are pressed down by about 0.124 Å. The adsorption energy of
Ni1 –Al(3) configuration is about 0.34 eV lower than that of Ni1 –Al(4)
configuration, whereas about 0.12 eV higher than that of Ni1 –O(5)
configuration.
If the Ni atom is positioned at the vertex of O(3) atoms, which is
considered as the initial configuration, then the final stable adsorp-
tion configuration will be same as that at the Al(4) site. If the Ni atom
is positioned at the vertex of Al(1) atoms, the final stable adsorption
configuration will be the same as that at the vacant O(5) three-fold
site, namely configuration Ni1 –O(5) . In this configuration, the Ni
atom should form bonds not only with three 3cO atoms, but also
(1) with 3cAl atoms on the surface through strong interaction. The 3cAl
atoms affected by Ni atom, namely the Al(1) atom, will be pressed
deeply under the surface and move down by 0.5 Å. This configura-
tion will become the one with maximal surface relaxation among
three possible configurations. At the same time, the Ni1 –O(5) con-
figuration shows the lowest adsorption energy among three stable
configurations, the energy difference can reach to 0.46 eV, as com-
pared with the most stable one. When the three cases are compared,
it can be found that the Ni atom tends to interact with the O atoms
(2) on surface, and is easily adsorbed on the multiple sites of the sur-
face. This result is rather similar to the adsorption state of Cu atom
on the ␣-Al2 O3 (0 0 0 1) surface, which is suggested by Hernández
et al. [19].
The electron population analysis results of the Ni atom and
␣-Al2 O3 are listed in Table 1. The Ni atoms in three config-
urations are all carried with positive charge, and the negative
charges of O atoms bonded with Ni atom all increase (except
the O(2)−2 atoms in Ni1 –O(5) configuration). In Ni1 –Al(4) con-
figuration, the positive charges of Al atoms interacted with
Ni atoms decrease, where as the positive charges of Al(3) and
Al(1) atoms interacted with Ni atoms in Ni1 –Al(3) and Ni1 –O(5)
 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107
Fig. 3. Stable configurations of single Ni atom on ␣-Al2 O3 (0 0 0 1).
Table 1
Adsorption energy and atomic Mulliken electron population data of Ni and relevant surface atoms for Ni adsorbed on the ␣-Al2 O3 (0 0 0 1) surface.
Configuration ENi
ads
(eV) Mulliken electron population data of different atoms (|e|)
3
Ni O(2)−1
Clean surface – – −0.915
Ni1 –Al(4) 3.91 0.662 −0.950
Ni1 –Al(3) 3.58 0.652 −0.923
Ni1 –O(5) 3.46 0.680 −0.951
increase to different extent. Because the Al(3) and Al(1) atoms
in these two configurations have experienced the second relax-
ation again, thus the interaction with adjacent oxygen atoms
will become stronger, and more positive charges can be car-
ried.
Except that the Al atoms in the configuration Ni1 –O(5) are pres-
sured under the surface due to larger relaxation, the Al atoms
on surface layer in configurations of Ni1 –Al(4) and Ni1 –Al(3) are
reduced to different extent, and carry less-positive charges. The
above results demonstrate that when the single Ni atom is adsorbed
onto the ␣-Al2 O3 (0 0 0 1) surface, it will lose electrons and carry
some positive charges, whereas the larger surface relaxation and
reconstruction can take place on the␣-Al2 O3 (0 0 0 1) surface, and
especially the relaxation of Al atoms on first layer is even more
obvious. At the same time, the negative charges carried by the oxy-
gen atoms increase, which suggests the possible charge transfer
between Ni atom and ␣-Al2 O3 .
It is known that the electron configuration of valence shell of
oxygen atom is 2s2 2p4 , that of Al atom is 3s2 3p1 , and that of single
Ni atom is 3d8 4s2 . In this work, the variations of state density for
every orbit before and after the adsorption of Ni atom in the most
stable adsorption structure Ni1 –Al(4) are investigated, in order to
distinguish the contribution of each orbit to the adsorption of Ni
atom. DOS data of the valence shell before and after the adsorption
of Ni atom on ␣-Al2 O3 surface are listed in Fig. 4, respectively. For
the structure Ni1 –Al(4) , the DOS peak height for Ni atom decreases,
and the DOS peak width increases simultaneously, which can result
in the cleavage of p orbitals of three O(2) atoms, as well as the large
overlapping between the d orbitals of Ni atom and the p orbitals of
O atom, suggesting the strong interaction between Ni atom and
␣-Al2 O3 surface. The peak for s orbital in DOS of Ni atom after
adsorption is diminished, while the partial peak shape for the s
99
O(2)−2 O(2)−3 Al(1) Al(3) Al(4)
−0.914 −0.913 1.196 1.622 1.620
−0.951 −0.950 1.174 1.612 1.608
−0.924 −0.923 1.187 1.663 1.598
−0.909 −0.938 1.249 1.624 1.600
orbit of O atom and the p orbit of Al atom can be more obvious,
which suggest that the electron transfer between Ni atom and the
atoms on the surface occurs.
3.2. Stable adsorption of Ni2 cluster on the surface of alumina
When the Ni2 binary cluster is adsorbed on the Al2 O3 (0 0 0 1)
surface, six possible stable adsorption configurations can be
obtained. The most stable adsorption configurations for horizontal
adsorption and vertical adsorption are shown in Fig. 5(a) and (b),
respectively. In the configuration (a) for horizontal adsorption, the
two Ni atoms of Ni2 cluster, named as Ni2−p,1 , will strongly interact
with the surface of alumina; Fig. 5(b) shows the most stable verti-
cal adsorption of Ni2 cluster, where only one Ni atom can interact
with the surface, the other will be pensile, named as Ni2−v,1. For the
configuration of horizontal adsorption, it can be concluded that the
two Ni atoms of Ni2 clustertend to bond with more atoms on sur-
face. Among these most stable configurations, the two Ni atoms are
located at the neighboring of the bridge sites of two 3-fold adsorp-
tion sites; In the stable vertical adsorption configuration calculated
in this work, one Ni atom in Ni2 cluster is adsorbed on the three
oxygen three-fold adsorption sites on the surface. The sequence of
adsorption stability of the Ni atom in Ni2 cluster on oxygen three-
fold adsorption sites is same as that of single Ni atom on the three
oxygen three-fold adsorption sites.
The electron population analysis data of Ni2 clusters and rel-
evant atoms on the Al2 O3 (0 0 0 1) surface are listed in Table 2.
For the configuration (a) of Fig. 5, the two Ni atoms carry with
partial positive charges, and the negative charges carried by the
oxygen atoms, which can bond with the two Ni atoms, decrease.
In structure (a), the Ni1 and Ni2 atoms can bond with the atoms
on surface, and the electrons would move toward surface, thus the
100 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107
Fig. 4. PDOS profiles of Ni atom and relevant atoms on Ni/␣-Al2 O3 (0 0 0 1) before adsorption (left) and after adsorption (right).
Table 2
Mulliken electron population data of stable adsorption configurations of Ni2 cluster on ␣-Al2 O3 (0 0 0 1) surface.
Configuration Mulliken electron population data of atoms (|e|)
Ni1 Ni2 O(2)−1
Bare – – −0.913
Ni2−p,1 0.372 0.385 −0.925
Ni2−v,1 0.296 –0.010 −0.964
two Ni atoms carry obvious positive charges. In the case of con-
figuration (b), the Ni atom interacted directly with surface carries
obvious positive charges, while the pensile Ni atom carries less neg-
ative charges. These facts demonstrate that the polarization of Ni2
cluster on Al2 O3 (0 0 0 1) can take place, and the interaction of two
Ni atoms with Al2 O3 (0 0 0 1) surface might be different. The strong
bonding effect of Ni1 atoms with the surface can result in obvious
positive charges as the several structures mentioned above. How-
ever, no obvious electron transfer between the pensile Ni2 atom
and surface can be found, the polarization effects will appear, so
that the Ni2 atom carries less negative charges. Gomes [9] studied
the property of the ␣-Al2 O3 (0 0 0 1) surface loaded with ␣-Al2 O3
(0 0 0 1) cluster with cluster model and periodic model respectively.
After analyzing local density of state (LDOS) and electron density,
he held that local polarization is the main cause of the combina-
tion of the two. Jung et al. [11] calculated the surface property of
noble metal loaded on ZrO2 surface with periodic DFT theory. And
he found that metal cluster M4 (Pt4 , Pd4 , Rh4 ) will be polarized on
the ZrO2 surface.
To deeply understand the bonding properties of atomic orbital
of metallic Ni, the PDOS profiles of the most stable configurations
of Ni2 cluster on surface (i.e. the horizontal and vertical adsorption)
are shown in Fig. 6.
O(2)−2 O(2)−3 O(2)−4 Al(1) Al(3)
−0.915 −0.914 −0.915 1.196 1.622
−0.930 −0.949 −0.946 – –
−0.958 −0.959 − – –
It can be found from Fig. 6(a)-1 and (a)-2 that the d orbital DOS
peak height of Ni1 and Ni2 atoms declines obviously, the energy
band is widened, the span of state density peak is widened, and
overlapping with the O atom orbital is also enlarged, which suggests
that the electron delocalization and the strong bonding effect of Ni
atom with the oxygen atoms on the surface. For the configuration
Ni2−v,1 , it can be found from Fig. 6(b)-1 that the d orbital of Ni1 atom
is obviously widened, overlapping with the p orbital of O atom. It
can even cause the electron density at Fermi-level to be close to 0,
and weaken the metallicity of Ni1 atom. Furthermore, the electron
density of Ni1 atom at Fermi-level is obviously less than that of
single Ni atom after adsorption, which suggests the addition of the
second Ni atom can improve the stability of the first Ni atom. In
Fig. 6(b)-2, the DOS peak shape of d orbital of Ni2 atom is relatively
narrow and high, with less overlapping with p orbital of O atom,
and the electron density at Fermi-level is very high, which indicates
the metallicity of Ni2 atom is stronger than that of Ni1 .
3.3. Stable adsorption of Ni3 cluster on the surface of alumina
There are two stable configurations of the isolated Ni3 ternary
cluster, including the regular triangular form and the beeline form.
The binding energy of triangular configuration is higher than that
 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107 101

Table 3
Adsorption energy, cluster formation energy and Ni–Ni bond length data of stable
configurations of Ni3 cluster adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

Configuration ENi
ads
(eV) ENi
clu
(eV) Ni–Ni bond length (Å)
3 3

L1 L2 L3

Ni3−c,1 5.40 3.39 2.311 2.312 2.522

Ni3−c,2 5.34 3.37 2.312 2.304 2.749
Ni3−c,3 5.11 3.29 2.357 2.336 2.366
Ni3−c,4 5.04 3.27 2.354 2.358 2.368
Ni3−c,5 4.87 3.21 2.342 2.340 2.321
Ni3−c,6 4.72 3.16 2.297 2.320 2.393

Table 4
Adsorption energy, cluster formation energy and Ni–Ni bond length data of stable
configurations of Ni3 cluster adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

Configuration ENi
ads
(eV) ENi
clu
(eV) Ni–Ni bond length (Å)
2 2

L1 L2

Ni3−L,1 4.69 3.24 2.360 2.468

Ni3−L,2 4.17 3.07 2.290 2.312
Ni3−L,3 4.06 3.03 2.290 2.494

Fig. 5. Stable adsorption configurations Ni2 clusters on ␣-Al2O3 (0 0 0 1) surface.
of linear one by 0.30 eV. In the first place, the initial adsorp-
tion configuration of Ni3 cluster is considered as the ternary ring
shape. After optimization, the six possible stable configurations are
obtained finally, named as Ni3−c,1 , Ni3−c ,2 , Ni3−c ,3 , Ni3−c ,4 , Ni3−c ,5
and Ni3−c ,6 , respectively (Fig. 7). The data on adsorption energy and
bond length for all the configurations are listed in Table 3. There
into the Ni3−c ,1 and Ni3−c ,2 are the most stable two structures, their
common characteristics is the existence of two Ni atoms located
at the two three-fold sites of Al(3) and Al(4) atoms, respectively,
which are the most stable adsorption sites for single Ni atom, and
the other will bond with the Al(1) atom on Al2 O3 (0 0 0 1) surface.
The main difference of both is that Ni3−c ,1 is adsorbed above the
O(2) atom while Ni3−c ,2 is adsorbed above the O(5) ternary site. In
the other four possible structures, the Ni3 cluster can be approxi-
mately parallel with the alumina surface, and three O atoms should
bond with three O atoms on Al(3) , Al(1) , Al(4) or O(5) sites separately.
As for the four horizontal adsorption configurations, the Ni-Ni bond
lengths in Ni3 cluster are very close, and thus the regular triangle
configuration can be maintained.
After studying adsorption configuration of ring-shape Ni3 clus-
ter, the adsorption of linear-form Ni3 cluster on ␣-alumina surface
is also investigated; the result is shown in Fig. 8. When the ini-
tial adsorption of Ni3 cluster is set to linear configuration, the
optimized three stable adsorption configurations can be obtained,
except that some of them will turn back to the ring-shape con-
figuration after optimization. Among these stable configurations,
the original linear configuration will be obviously curled. The data
on adsorption energy of three configurations are less than those of
any previous configurations. The data in Table 4 indicate that the
adsorption with two fold line shapes should be apparently more
stable than that with the third nearly straight line shape. However,

Fig. 6. PDOS profiles of most stable configurations of Ni2 cluster on ␣-Al2 O3 (0 0 0 1) surface (a) Ni2−p ,1 and (b) Ni2−v,1 .
102 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107

Table 5
The Mulliken electron population data of concerned atoms with Ni3 cluster adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

Configurations Mulliken electron population of atoms (|e|)

Ni1 Ni2 Ni3 O(2)−1 O(2)−2 O(2)−3 O(2)−4 O(2)−5 Al(1) Al(3)

Ni3−c,1 0.380 0.373 −0.161 −0.967 −0.955 −0.931 −0.921 −0.945 1.265 1.670
Ni3−c,2 0.423 0.406 −0.218 −0.973 −0.963 −0.941 −0.921 −0.936 1.329 1.659
Ni3−c,3 0.271 0.284 0.273 −0.943 −0.944 −0.944 – – – –
Ni3−c,4 0.263 0.276 0.272 −0.939 −0.939 −0.939 – – – –
Ni3−c,5 0.277 0.269 0.264 −0.951 −0.952 −0.949 – – – –
Ni3−c,6 0.273 0.269 0.267 −0.940 −0.951 −0.944 – – – –
Ni3−L,1 0.426 0.118 0.371 −0.942 −0.945 −0.933 −0.956 −0.949 – –
Ni3−L,2 0.436 0.137 0.145 −0.946 −0.952 −0.956 −0.916 – 1.271 –
Ni3−L,3 0.402 0.122 0.164 −0.945 −0.942 −0.935 −0.929 1.225 –

the adsorption energy for the most stable configuration Ni3−L ,1
is still lower than that of the sixth ring-shape configuration by
0.03 eV.
Electron population data of all concerned atoms for the on sur-
face adsorbed Ni3 clusters with ring and linear form configurations
are listed in Table 5. It is found that the total charge on Ni atoms
is always positive, i.e. the Ni3 cluster will lose some electrons.
In most stable two ring-shape adsorption configurations, the Ni3
atoms bonded with Al(1) atoms on surface carry negative charges,
whereas the Ni1 and Ni2 atoms bonded directly with O atoms on
surface all carry positive charges.
The electronic configuration of Ni atom is 3d8 4s2 , and its d
orbital is electron unsaturated, which can afford the dual abilities
to accept and provide electrons to the Ni atom. The Al(1) atom on
alumina surface is of unsaturated coordination bond, and thus it
can provide electrons to Ni3 atoms. The unsaturated O(2) atom on
the surface can accept electrons transferring from Ni3 cluster. After
Ni atom is adsorbed on alumina surface, the d orbitals of Ni1 and Ni2
atoms bonded directly with oxygen atoms on the surface will over-
lap with the p orbital of oxygen atom, the electrons will transfer
from Ni atoms to the surface. The hybridization between d orbital
of Ni3 atom and Al(1) atom takes place, and the electrons transfer
from Al(1) atom to Ni3 atom. For the other four adsorption config-
urations, each Ni atom can bond only with one O(2) atom on the
surface, the d orbital of Ni atom overlaps with the p orbital of O
atom, and thus the Ni atoms in the four configurations similarly
carry positive charges.
When the linear Ni3 cluster is adsorbed on the surface, three Ni
atoms carry positive charges because of bonding with the oxygen
atom on the surface. The sum of positive charges is equal to that
of the horizontal adsorption of ring shape Ni3 cluster. However, the
adsorption energy of linear adsorption is much less than that of the
ring shapes adsorption. Therefore, the interaction between Ni–Ni
bonds is also one of important factors affecting adsorption stability.
After the Ni3 cluster is adsorbed on alumina surface, the interaction
of Ni–Ni atoms and that of Ni-surface influence each other and com-
pete with each other. When the linear Ni3 cluster is adsorbed on
the surface, although three Ni atoms can bond with the atoms on
surface, the distance between Ni–Ni atoms increases and the inter-
action of Ni–Ni atoms is weakened, and the stability of adsorption
configuration is weaker.
3.4. Stable adsorption of Ni4 quaternary cluster on ˛-Al2 O3
(0 0 0 1) surface
When the initial adsorption configurations of Ni4 cluster are
all set to regular tetrahedron, the seven stable adsorption config-
urations are obtained after optimization (as is shown in Fig. 9),
which are named as Ni4−t,1 , Ni4−t,2 , Ni4−t,3 , Ni4−t,4 , Ni4−t,5 , Ni4−t,6
and Ni4−t,7 , respectively. The configuration Ni4−t , 1 (Fig. 9(a)) is
the most stable among the seven configurations. The Ni1 and Ni2
atoms can bond separately with two O(2) atoms on the surface, and
another Ni3 atom at the bottom will bond with one O(2) atom.
At the same time, the Ni2 and Ni3 atoms bond with Al(1) atom
on the surface. The Al(1) atom is pressed below the surface, and
the endocentric relaxed distance is 0.655 Å. In the five structures
of a, b, c, e and g, the one side of tetrahedron bonds with the
surface, and the fourth Ni atom does not interact with the alu-
mina surface directly. Except the case e, where the Ni4 cluster
is more deformed, the Ni4 clusters in other four structures can
keep their original tetrahedral structure. The difference between
the cases d or f with other structures is that the Ni4 cluster stays
on the surface by one edge of tetrahedron. Ni1 and Ni2 atoms are
located at two O three-fold sites of Al(3) and Al(4) atoms, and Ni3
atom bonds with Al(1) atom on the surface. Ni1 and Ni2 atoms are
at the dual oxygen bridge sites by the two three-fold sites, and
Ni1 and Ni3 atoms bond with Al(1) atom on the surface simulta-
neously. In the configurations of d and f, the cluster Al(1) atoms
bonded with Ni atom will relax outwards to different extent, and
the Al(1) atoms will be pulled outwards by 0.277 Å and 0.331 Å,
respectively.
In this work, the adsorption of Ni4 cluster, whose initial adsorp-
tion configuration is a plane, is also investigated. In the selected
configurations, only the few optimized structures are the same
as the initial tetrahedral structure, most of the other structures
can keep the plane configuration. The whole Ni4 cluster plane is
parallel with the alumina surface (except for the most stable pla-
nar adsorption configuration, only the optimized planar as well as
stereo structures are listed in Figs. 3–12). Among the most stable
planar adsorption configuration (Fig. 9(h), named as Ni4−f,1 ), the
bottom consisting of three Ni atoms is parallel with alumina sur-
face. The three Ni atoms can bond with O atoms on the alumina
surface separately, and the position of Ni4 atom is higher than that
of other Ni atoms. Ni4 atom will bond with one Al(1) atom of on
the alumina surface, forming a chair-like structure. In the struc-
ture, the surface will also undergo larger relaxation. Influenced
by Ni atom, the Ni4 atom bonded with Al(1) atom is pulled up by
0.387 Å.
The data on the adsorption energy of stable Ni4 clusters and
the Mulliken electron population of relevant atoms on the alu-
mina surface are listed in Table 6. It can be found that even the
adsorption energy for the most stable planar configuration of Ni4
cluster is still lower than those of the most stable five steric con-
figurations. To achieve the stable configuration, the original planar
configurations are greatly changed, and the Ni4 atom is lifted up,
bonding with the unsaturated coordinated Al(1) atom on the sur-
face, the Ni4 atom accepts electrons, and thus carries obvious
negative charges.
Such deactivation problems as coking and sintering exist in
Ni-based catalyst. Thus, improving the stability of Ni-based cat-
alyst is the key to achieve industrialization of methane partial
oxidation [7]. Yu et al. [20] studied four kinds of catalysts of
methane partial oxidation to syngas: i/␥-Al2 O3 , Ni/␦-Al2 O3 , Ni/␪-
Al2 O3 and Ni/␣-Al2 O3 . Results showed that there was apparent
 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107 103

Fig. 7. Stable configuration diagrams of Ni3 clusters adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

Table 6
Adsorption energy, cluster formation energy and Mulliken electron population data for the Ni4 cluster stably adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

Configurations ENi
ads
(eV) ENi
clu
(eV) Mulliken electron population of atoms (|e|)
4 4

Ni1 Ni2 Ni3 Ni4 Al(1) Al(3)

Ni4−t,1 5.76 3.32 0.403 0.411 0.260 −0.082 1.455 –

Ni4−t,2 5.72 3.31 0.370 0.410 0.228 −0.063 – –
Ni4−t,3 5.47 3.25 0.379 0.355 0.228 −0.062 – –
Ni4−t,4 5.45 3.24 0.383 0.373 0.010 −0.062 1.220 1.677
Ni4−t,5 5.42 3.23 0.341 0.418 0.372 −0.094 1.377 –
Ni4−t,6 5.22 3.19 0.295 0.295 0.017 −0.068 1.319 –
Ni4−t,7 5.06 3.15 0.271 0.274 0.283 −0.053 – –
Ni4−f,1 5.29 3.29 0.401 0.446 0.216 −0.192 1.247 –

characteristic peak of NiAl2 O4 in the sample using ␥-Al2 O3 as
the carrier. However, it is not easy for Ni and ␣-Al2 O3 to form
Ni–Al spinel. Jacono et al. [21] studied the interaction between
Ni2+ and ␥-Al2 O3 , and they found that Ni–Al spinel exists on
the surface of Al2 O3 . Ren et al. [22] pointed out that almost all
of the catalyst treated with high temperature is NiAl2 O4 , which
is inactive for methane partial oxidation reaction under certain
conditions, because of the strong interaction between Ni and
Al2 O3 .
Yan et al. [23] found that with the size of Ni/␣-Al2 O3 decreas-
ing, that is, when the dispersion of the active component was
enhanced, and growth of Ni grain was inhibited at high temper-
ature, the stability of catalytic active component can be improved.
Zhu et al. [5] conducted methane partial oxidation to syngas
reaction using CeO2 as the carrier loaded with Ni. They thought
that the high dispersion of Ni on CeO2 contributes to the trans-
fer of O from CeO2 to Ni and thus the carbon species generated
in methane decomposition can be effectively oxidized. The size
of Ni grain plays a key role in the stability of the catalyst: the
smaller the grain is, the better the stability of the active center
is.
In this paper, the interaction between Ni and ␣-Al2 O3 was
examined to analyze the catalytic activity and catalyst structure.
Meanwhile, the following study of our research team is being con-
ducted, for example, the stability and activity of the catalyst is
enhanced by adding additives. The study results of this paper can
be used as comparison to provide support for improving the per-
formance of the catalyst.
104 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107

Fig. 8. Adsorption configuration diagrams of linear Ni3 cluster adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

3.5. Migration and aggregation of Ni atoms on the surface
When the Ni atom is supported on the alumina surface, the
interaction between metal atoms and surface and that between
metal atoms plays an essential role for the stability of the whole
system. Principles of the spontaneous monolayer distribution hold
that the active component of many supported catalysts will dis-
perse spontaneously onto the surface of the carrier. Methane partial
oxidation reaction may occur on active center with 3 or 4 Ni atoms
[24,25]. Meanwhile, the less the Ni atoms of the active center is,
 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107 105

Fig. 9. Stable configurations of Ni4 cluster adsorbed on ␣-Al2 O3 (0 0 0 1) surface.

the better stability of the catalyst is [23,25]. The course that sin-
gle Ni atom transfers on the carrier surface and then unites was
examined and the difficulty extent of the formation of the active
center as studied. Thus, the catalytic performance of the catalyst
was assessed. To study the diffusion properties of metal Ni atoms
on alumina surface, the diffusion activation energy of single atom
on surface is investigated. According to the discussion above, it is
known that there exist three stable adsorption sites of Ni atom
on ␣-Al2 O3 surface, i.e. the three-fold sites for Al(4) , Al(3) and O(5)
atoms. The transitional states for diffusion of Ni atom onto sites
and those from one site to adjacent one are separately investigated.
The transitional configurations for the two processes are shown in
Fig. 10.
In Fig. 11, NiO(5) , NiAl(3) and NiAl(4) separately stand for the
structures of Ni atoms adsorbed at the three three-fold adsorp-
tion sites of O(5) , Al(3) and Al(4) . It can be seen from the figure that,
after the adsorption of Ni atom on alumina surface, the energy
level greatly decreases, and thus the relatively stable adsorp-
tion structure can be formed. There are three adsorption sites
for Ni atoms on alumina surface, and the transitional states of
Ni atom migrating between these sites are named as TS1 and
TS2. When a Ni atom migrates from one site to adjacent one,
the barrier of 11.4 kJ/mol is stridden over, while the barrier of
41.9 kJ/mol is necessary for the migration from site to site. The
activation energy of the two migration processes is much lower
than the adsorption energy on alumina surface, which suggests
106 M. Zhang et al. / Applied Surface Science 287 (2013) 97–107

Fig. 10. Diffusion process of Ni atom on the ␣-Al2 O3 surface (a) O (5) site → Al (3) site; (b) Al (3) site → Al (4) site.

Ni+S the Ni atoms to migrate. The better understanding on the interac-

0
tion between the carrier surface and metal cluster can provide not
only theoretical basis to further research on the physico-chemical
-50
structures and catalytic properties of supported solid catalyst, butal
-100 so some instructions to design and develop novel effective catalyst
system.
Relative Energy(kJ/mol)

-150

-200 References

-250
TS1 TS2
-300
NiO(5) NiAl(3)
41.9
-350 11.4 NiAl(4)
-400
Fig. 11. Transitional states of Ni atoms migrated on ␣ alumina surface.
that the migration of Ni atom on alumina surface is very easy to
occur.
4. Conclusion
Using the quantum chemistry computation based on DFT theory,
the stable adsorption sites of Ni atoms supported on the ␣-Al2 O3
(0 0 0 1) surface are calculated. It can be concluded that there exist
three kinds of stable adsorption sites on the surface for the single Ni
atom; the oxygen three-fold vacant site is the preferable adsorption
site. With the increase of Ni atom number, the preferable adsorp-
tion site on alumina surface becomes indefinite gradually, i.e. there
exists no definite preferable adsorption site for the multiple Ni clus-
ter on alumina surface. When the Ni cluster is adsorbed on the
alumina surface, the obvious electron transfer between Ni cluster
and ␣-Al2 O3 (0 0 0 1) surface can occur, and the Ni clusters com-
bine with ␣-Al2 O3 surface through local polarization. The diffusion
activation energy of Ni atom from one stable site to another on alu-
mina surface is relatively low, suggesting that it is rather easy for
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