Chemical Physics Letters 657 (2016) 11–17

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Chemical Physics Letters

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

Research paper

DFT study of the adsorption properties of single Pt, Pd, Ag, In and Sn on
the c-Al2O3 (1 1 0) surface
Hongwei Gao
Key Laboratory of Plant Resources and Chemistry in Arid Regions, Xinjiang Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Urumqi 830011, China

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

Article history: GGA/PW91 exchange–correlation functional within periodic density functional theory (DFT) has been
Received 31 March 2016 used to investigate the adsorption properties of different metal atoms (Pt, Pd, Ag, Sn and In) on the
In final form 25 May 2016 O-terminated and Al-terminated c-Al2O3 (1 1 0) surface. The predicted adsorption energies follow the
Available online 25 May 2016
order Sn > In > Ag > Pd > Pt. It is found that O-bridge position is the most favorable site for single Pt,
Pd, Ag, Sn and In adsorption on the O-terminated c-Al2O3 (1 1 0) surface. It is found that the most
Keywords: favorable site on the Al-terminated c-Al2O3 (1 1 0) surface is O-top position.
DFT
Ó 2016 Elsevier B.V. All rights reserved.
Catalyst
Pt/c-Al2O3
Adsorption properties
(1 1 0) surface

1. Introduction
c-Al2O3 is the one of the most widespread supports in heteroge-
neous catalysis for the selective catalytic reduction of NOx by
hydrocarbons (HC-SCR) [1–3]. It is well-known that the interaction
of single Pt, Pd, Ag, In and Sn with the support of c-Al2O3 plays an
important role on the activity of the heterogeneous catalysts [4].
Both theoretical and experimental methods have been extensively
used to explore the structure and properties of single Pt, Pd, Ag, In
and Sn with the support of c-Al2O3, respectively.
A recent research article by Lira revealed the structure and
chemical state of Pt supported on c-Al2O3 during the oxidation of
NO using X-ray absorption near-edge spectroscopy and extended
X-ray absorption fine-structure spectroscopy [5]. Stability and
activity of Pd/Al2O3, Pt/Al2O3 and Pd–Pt/Al2O3 catalysts for NO
oxidation was investigated in flow reactor. They found that
Pd–Pt/Al2O3 catalyst has higher NO oxidation activity than
Pd/Al2O3 or Pt/Al2O3 because of the interaction between Pt and
Pd [6]. Photoelectron spectroscopy (XPS) and extended X-ray
absorption fine structure spectroscopy (EXAFS) was used to study
the nature of silver species on c-Al2O3 with different silver load-
ings [7]. Selective catalytic reduction of NOx with propene by Liu
[8] confirmed that SnO2/Al2O3 and In2O3/Al2O3 exhibited higher
NOx conversion than Ag/Al2O3 and Co/Al2O3 because of the high
E-mail address: gaohongw369@ms.xjb.ac.cn
surface area and the strong interaction between SnO2 or In2O3
and Al2O3. The thermodynamic stability of CxHy species formed
upon dissociative adsorption of ethane on Pt13/c-Al2O3 was
reported by DFT calculation [9]. In situ diffuse reflectance infrared
Fourier transform spectroscopy (DRIFTS) and Density functional
theory (DFT) have been used to investigate the adsorption of acet-
ate species (CH3COO
) on the Ag/Al2O3 [10].
The interaction between the nanoclusters and their support
plays a very important role and is considered to be crucial to the
catalytic properties of many metal-catalysts. However, the corre-
sponding stability and diffusion trend of single Pt, Pd, Ag, In and
Sn on the c-Al2O3 (1 1 0) surface remain unresolved. The challenge
of the present work is to explore the stability and diffusion trend of
different metals on the c-Al2O3 (1 1 0) surface. The nature of the
formation of single Pt, Pd, Ag, In and Sn on the c-Al2O3 (1 1 0) sur-
face is still mysterious and plentiful details remain to be uncov-
ered. Herein lies our motivation for optimizing structures,
calculating the adsorption energy and analyzing electronic config-
urations to unveil the reaction mechanism of metal with catalytic
surface. This work will provide a useful benchmark for future
investigations on the metal-catalysts.
The aim of the present work is to apply the DFT method to study
the adsorption properties of single Pt, Pd, Ag, In and Sn on the
c-Al2O3 (1 1 0) surface, including adsorption energy and electronic
configurations. A fundamental understanding of the adsorption
properties of different metals on the c-Al2O3 (1 1 0) surface is
believed to be essential for the development of a metal/c-Al2O3
catalyst and improvement for its potential application.

http://dx.doi.org/10.1016/j.cplett.2016.05.056
0009-2614/Ó 2016 Elsevier B.V. All rights reserved.
12 H. Gao / Chemical Physics Letters 657 (2016) 11–17

Table 1 the d-type polarization functions) with fine precision was

Adsorption energy eads (eV) for Pt, Pd, Ag, In, Sn on c-Al2O3 (1 1 0) surface at employed for geometry optimization and properties calculation.
GGA/PW91 level.
The convergence criteria applied during geometry optimization
Site Pt Pd Ag Sn In and properties is 1.0  10
6 Ha for energy, 0.002 Ha/Å for max.
O-terminated surface force and 0.005 Å for max. displacement. The quality of global orbi-
O-top
0.81
0.96
0.96
3.28
3.40 tal cutoff is set as fine of 5.0 Å. On the basis of the convergence test
O-bridge
2.31
2.92
3.19
12.27
5.07 for k-point sampling, the k-point set of (4  4  4) is used for the
Al-top
1.76
1.46
1.81
5.47
5.26
Al-bridge
1.66
1.80
1.64
5.04
4.96
calculation of single Pt, Pd, Ag, In and Sn on c-Al2O3 (1 1 0) surface.
A slab model of 5 atomic layers with a 4  4 surface supercell
Al-terminated surface
O-top
3.59
5.58
3.73
7.59
7.64
was built for c-Al2O3 (1 1 0) surface in this work. This slab model
O-bridge
3.73
3.69
3.38
6.09
5.80 contains 184 atoms and has a vacuum gap of 15 Å. The top two lay-
Al-top
4.00
3.33
2.34
5.94
5.85 ers were relaxed and the bottom three layers were fixed at their
Al-bridge
0.13
3.87
3.11
5.41
5.75 fractional position during the process of geometry optimization.

2. Computational methods 3. Results and discussion

We performed DFT calculations with the Dmol3 program [11,12]
in the Material Studio (MS) of Dassault Systèmes Biovia Corp. The
Becke exchange [13] plus Perdew–Wang approximation functional
[14] within Generalized gradient approximation (GGA) was used in
all calculations. The DND basis set (double numerical basis set with
3.1. Adsorption of single Pt, Pd, Ag, In and Sn on the O-terminated
c-Al2O3 (1 1 0) surface
The most abundant exposed surface of c-Al2O3 is (1 1 0) termi-
nation and this surface remains dehydrated in usual experimental

Fig. 1. Top view of optimal Pt adsorption structure on the O-terminated c-Al2O3 (1 1 0) surface: (A) O-top, (B) O-bridge, (C) Al-top, (D) Al-bridge. Pt, O and Al atoms are
represented as blue, red and magenta spheres, respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
 H. Gao / Chemical Physics Letters 657 (2016) 11–17 13

conditions according to the literatures [15–17], therefore the dehy-
drated c-Al2O3 (1 1 0) surface was established using MS Dmol3
interface. To explore the effect on adsorption energy for exposed
atoms on the surface, we built O-terminated and Al-terminated
surfaces.
In order to compare the structure stability, the adsorption
energy (Eads, eV) of single Pt, Pd, Ag, In and Sn on the c-Al2O3
(1 1 0) surface was calculated as follows [18]:
Eads ¼ EðsurfaceþadsorbateÞ
ðEsurface þ Eadsorbate Þ
where E(surface+adsorbate) is the total energy of the surface of c-Al2O3
(1 1 0) with adsorbate, Esurface is the total energy of the surface of
c-Al2O3 (1 1 0), and Eadsorbate is the total energy of adsorbate.
The Pt adsorption energies at the O-top, O-bridge, Al-top and Al-
bridge positions on the O-terminated c-Al2O3 (1 1 0) surface are

0.81,
2.31,
1.76 and
1.66 eV/atom, respectively (see Table 1).
The most favorable site for Pt adsorption on the O-terminated
c-Al2O3 (1 1 0) surface is O-bridge position. The similar trend was
also found for Pd, Ag and Sn adsorption on the O-terminated
c-Al2O3 (1 1 0) surface: O-bridge position is the most favorable site.
The calculated energies for the O-bridge adsorption of Pt, Pd, Ag,
Sn and In on the O-terminated c-Al2O3 (1 1 0) surface are
2.31,

2.92,
3.19,
12.27 and
5.07 eV/atom, respectively (see
Table 1). Obviously, the adsorption energies of Sn and In are much
larger than ones of Pt, Pd and Ag, which is in very good agreement
with the experiment about SnO2/Al2O3 and In2O3/Al2O3 being a
type of lean deNOx catalyst.
We performed a geometry optimization with the same accuracy
criterion for the Pt, Pd, Ag, Sn and In adsorption structures on the
O-terminated c-Al2O3 (1 1 0) surface with the geometry optimiza-
tion for the c-Al2O3 (1 1 0) surface. The optimized adsorption struc-
tures are show in Fig. 1. The optimized bond distance of Pt–O in the
O-top site is 2.543 Å, which is in good agreement with the experi-
mental value of 2.50 Å [5]. The calculated distance between the Pt
atom and the Al atom in the Al-top site is 2.74 Å, whereas the cal-
culated Pt–Al bond distance reported by Zhou is 2.415 Å [19]. The
optimized bond distance of Pd–O in the O-top site is 2.545 Å, which
is close to the DFT result of 2.65 Å in the literature [20].
3.2. Adsorption of single Pt, Pd, Ag, In and Sn on the Al-terminated
c-Al2O3 (1 1 0) surface
The adsorption energies for Pt, Pd, Ag, In and Sn at the O-top,
O-bridge, Al-top and Al-bridge positions on the Al-terminated

Fig. 2. Top view of optimal Pt adsorption structure on the Al-terminated c-Al2O3 (1 1 0) surface: (A) O-top, (B) O-bridge, (C) Al-top, (D) Al-bridge. Pt, O and Al atoms are
represented as blue, red and magenta spheres, respectively. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
14 H. Gao / Chemical Physics Letters 657 (2016) 11–17

Fig. 3. Calculated PDOS for Pt, Pd, Ag, Sn, In, O and Al for O-bridge site on the O-terminated (1 1 0) surface.
 H. Gao / Chemical Physics Letters 657 (2016) 11–17 15

Fig. 4. Calculated PDOS for Pt, Pd, Ag, Sn, In, O and Al for O-top site on the Al-terminated (1 1 0) surface.

c-Al2O3 (1 1 0) surface were found to be much larger than the ones
on the O-terminal surface. The most favorable site on the
Al-terminated c-Al2O3 (1 1 0) surface is O-top position.
Adsorption energies in Table 1 reveals the following trends: Pt,
Pd, Ag, Sn and In adsorptions are more favorable on Al-terminated
surface than on O-terminated surface. The Sn-c-Al2O3 and
In-c-Al2O3 interactions are much stronger than Pt-c-Al2O3,
Pd-c-Al2O3, and Ag-c-Al2O3 interactions.
The Pt, Pd, Ag, Sn and In adsorption structures on the Al-
terminated c-Al2O3 (1 1 0) surface are show in Fig. 2. The optimized
16 H. Gao / Chemical Physics Letters 657 (2016) 11–17

Table 2 Al atom. This is also in good agreement with our adsorption energy
Mulliken charge (e) for Pt, Pd, Ag, In, Sn on c-Al2O3 (1 1 0) surface at GGA/PW91 level. calculations.
Site Pt Pd Ag Sn In The PDOS in Fig. 4 shows the overlap of O-2p with Pt-5d9, Pd-
O-terminated surface 4d and Ag-4d10, which suggests there is a charge transferred
10

O-bridge 0.03 0.065 0.110
0.021
0.002 from the empty d orbital of Pt, Pd and Ag, to O and the interaction
O1 at O-bridge
0.735
0.735
0.735
0.737
0.736 of these metals with the surface O atom. The bands near the Fermi
O2 at O-bridge
0.653
0.654
0.658
0.648
0.659 level were mainly contributed to the Sn-5p6, In-5p1, Al-3s2 and
Al-terminated surface Al-3p1 states. Sn-5p and In-5p1 hybridize significantly with the
O-top
0.251
0.188
0.120
0.309
0.304 Al-3s2 and Al-3p1 showing strong covalent contribution.
Al1 at O-top 0.772 0.743 0.724 0.847 0.825
Al2 at O-top 0.417 0.419 0.415 0.424 0.431
3.5. Population analysis for Pt, Pd, Ag, Sn and In absorbed at O-bridge
site on the O-terminated (1 1 0) surface and at O-top site on the
Al-terminated (1 1 0) surface
Pt–O bond distance in the Al-top site is 2.636 Å, which is little
larger than the experimental value of 2.50 Å. The optimized Pd–O To gain further insight into the nature of bonding, we report a
bond distance in the O-top site is 2.691 Å, which is in agreement comparison of Mulliken charges for Pt, Pd, Ag, Sn and In absorbed
with the DFT result of 2.65 Å. During optimization process, Pt bent at O-bridge site on the O-terminated (1 1 0) surface and at O-top
a lot to form a Al–O–Al bridging position. Similar trend also was site on the Al-terminated (1 1 0) surface in Table 2.
found for Pd, Ag, Sn and In adsorption on the Al-terminated O-bridge site is the most stable position for Pt, Pd, Ag, Sn and In
c-Al2O3 (1 1 0) surface. absorbed on the O-terminated (1 1 0) surface. For O-bridge site on
the O-terminated (1 1 0) surface, Pt, Pd and Ag atoms have the
positive charge of 0.03, 0.065 and 0.110 e, respectively. However,
3.3. Analysis of Partial Density of States (PDOS) for Pt, Pd, Ag, Sn and In
the calculated Mulliken charge of Sn and In have the negative values
absorbed at O-bridge site on the O-terminated (1 1 0) surface
of
0.021 and
0.002 e. Obviously, the surface O always gains charge
density from Pt, Pd and Ag, but it gives charge density to Sn and In.
In order to find the contribution of atomic orbital to the density
For O-top site on the Al-terminated (1 1 0) surface, the calcu-
of states (DOS), we have plotted PDOS of the different orbitals (s, p
lated Mulliken charge of Pt, Pd, Ag, Sn and In have the negative val-
and d) from Pt, Pd, Ag, In, Sn, Al and O. PDOS for Pt, Pd, Ag, In and Sn
ues of
0.251,
0.188,
0.120,
0.309 and
0.304 e, respectively,
adsorption at O-bridge site on the O-terminated c-Al2O3 (1 1 0) sur-
which illustrate that these metals gain charge density from the
face are show in Fig. 3.
surface Al. Sn and In gains much more charge density from the sur-
Electronic configurations are considered in this part: For Pt[Xe]
face Al than Pt, Pd and Ag.
4f145d96s1, Pd[Kr]4d10, Ag[Xe]4d105s1, Sn[Kr]4d105s25p6 and In[Kr]
Population analysis shows the following trend: Sn and In have
4d105s25p1, the 4f145d96s1, 4d10, 4d105s1, 4d105s25p6, and
the bigger impact on the surface Al or O atom than Pt, Pd and Ag
4d105s25p1 electrons are considered as the true valence, respec-
at the most stable position on O-terminated (1 1 0) surface or Al-
tively. For Al[Ne]3s23p1, 3s23p1 electron states is treated as valence
terminated (1 1 0) surface.
states. For O, only the true valence states (2s22p4) are taken into
account, because these states are enough to have the correct trans-
ferability property. 4. Conclusions
In Fig. 3, it can be obviously seen that the band at
0.75 eV was
mainly controlled by the O 2s state. For O 2p state, the band is In this work, the adsorption mechanisms of single Pt, Pd, Ag, Sn
wide, which is hybridized with the Pt-5d, Pd-4d, Ag-4d and Sn-5s and In on the O-terminated and Al-terminated c-Al2O3 (1 1 0) sur-
states. The coupling of Pt, Pd and Ag with the surface O have the face have been investigated and compared. The interactions of sin-
appreciable d character, but for Sn, only sp character is observed. gle Pt, Pd, Ag, Sn and In with the surface O and Al have been
The bands near the Fermi level were mainly contributed to the analyzed by adsorption energy, PDOS and Mulliken charges. Single
Pt-6s, Pd-4s, Ag-5s, Sn-5p, In-5p, Al-3s and Al-3p states. Sn-5p Pt, Pd, Ag, Sn and In adsorption prefer O-bridge on the
band extending over wider energy ranges has the higher density O-terminated c-Al2O3 (1 1 0) surface and O-top position on the
of states and hybridize significantly with the Al-3s and Al-3p Al-terminated c-Al2O3 (1 1 0) surface. These two most favorable
showing strong covalent contribution. This phenomenon can adsorption positions have been explained by the different
explain why Sn has the highest adsorption energy in the Pt, Pd, electronic configuration of single Pt, Pd, Ag, Sn, In, the surface Al
Ag, Sn and In adsorptions at O-bridge site on the O-terminated and the surface O. The coupling of Pt, Pd and Ag with the surface
(1 1 0) surface. O have the appreciable d character, but for Sn and In, only sp char-
acter is observed.

3.4. Analysis of PDOS for Pt, Pd, Ag, Sn and In absorbed at O-top site on
the Al-terminated (1 1 0) surface
Fig. 4 shows PDOS of single Pt, Pd, Ag, In and Sn adsorbed on the
Al-terminated c-Al2O3 (1 1 0) surface.
As single Pt, Pd, Ag, In and Sn atom interact with the
Al-terminated c-Al2O3 (1 1 0) surface, the valence electrons of Pt,
Pd, Ag, In and Sn overlap with the lowest unoccupied molecular
orbital (LUMO) of the surface O or Al. The more negative the LUMO
of the surface O or Al, the more easy the electrons of Pt, Pd, Ag, In
and Sn were trapped in the LUMO. The O atom has the lower LUMO
energy than the Al atom, therefore, the surface O atom binds stron-
ger than the surface Al atom with the valence electrons of Pt, Pd,
Ag, In and Sn. The surface O atom is more reactive than the surface
Acknowledgements
This work was financially supported by Recruitment Program of
Global Experts. This work was also financially supported by the
Director Foundation of XTIPC, CAS, Grant No. 2015RC011.
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