Surface Science 605 (2011) 489–493

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Surface Science
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u s c

Formation of sulfite-like species on Cr2O3 after SO2 chemisorption

V.A. Ranea a, S.N. Hernandez b, S. Medina b, I.M. Irurzun a, I.D. Coria b, E.E. Mola a,b,⁎
a
CCT-La Plata-CONICET, Instituto de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad Nacional de La Plata, Calle 64 y Diagonal 113,
1900 La Plata, Argentina
b
Facultad de Química, e Ingeniería, Pontificia Universidad Católica Argentina, Mendoza 4197 CP 2000 Rosario, Argentina

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

Article history: The adsorption of sulfur dioxide (SO2) on polycrystalline Cr2 O3 was experimentally investigated using
Received 9 September 2010 temperature-programmed desorption (TPD). The chemisorption of SO2 on the (0001) surface was also
Accepted 3 December 2010 studied using theoretical methods. Different adsorption geometries were explored for SO2 adsorption on the
Available online 13 December 2010
α-Cr2 O3 (0001) surface. Two similar adsorption configurations were found to be the most stable with
chemisorption energies of − 3.09 and − 2.79 eV/molecule. In both calculated stable adsorption configurations
Keywords:
Density functional calculations
the appearance of sulfite-like species is predicted on the (0001) surface after adsorption. It is important to
Chemisorption emphasize that these results are predicted only within the DFT + U framework. Under these conditions and
Thermal desorption despite great efforts, no stable sulfate-like geometry was found on this surface. The TPD spectrum exhibit a
Sulfur dioxide desorption peak at Tp ≈ 870 °C with a heating rate of β ≈ 0.12 °C/s. The desorption energy calculated by the
Polycrystalline surfaces analysis given by Redhead and Adams, assuming the rate of desorption is given by a Polanyi–Wigner equation,
Low index single crystal surfaces is ≈ − 3.12 eV. This value is in good agreement with the predicted one using DFT + U calculations. To our
Solid-gas interfaces knowledge, this is the first theoretical study of SO2 adsorption on the Cr2 O3 (0001) surface.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction The α-Cr2 O3 (0001) has been experimentally investigated using

The metal oxide surfaces are of great interest in topics such as
catalysis and corrosion. Environmental science has received much
attention and catalytic surfaces have been used in order to eliminate
harmful molecules (such as SO2, NH3, CO and NOx) from air due to
pollution. Among these molecules, SO2 is one of the products emitted
to the atmosphere from natural and human sources that can be
converted into acid rain. Most of the SO2 that reach the atmosphere
(≈3/4) is produced by human activities, mainly, the combustion of
fossil fuels. More than half of the world production comes from a few
developed countries.
Looking for the best surface to capture SO2, its adsorption has been
investigated on several selected polycrystalline transition metal
oxides (Co, Ni, Fe, V, Mn, Cr and Mo) supported on alumina [1]. At
high temperature, Cr2 O3 is the oxide with the maximum capacity to
adsorb SO2. Compounds formation on the surface and the desorption
process have also been investigated. The surface can be regenerated
by an 800 °C air passing treatment, and can recover its original
adsorption capacity. It is proposed in that article [1] that the SO2
retention on the Cr2 O3 surface is a chemisorption process with sulfite
formation on the surface.
different techniques such as low energy electron diffraction (LEED)
and scanning tunneling microscopy (STM) [2–5]. The surface is
Chromium-terminated and undergoes profound vertical relaxations
of the external layers without lateral distortions. Different theoretical
approaches have also been used to study chromia as well as the
α-Cr2 O3 (0001) surface [6–11]. There is a general agreement among
the different methodologies that the surface undergoes strong vertical
relaxations. In this article we take into account the strong electron
correlation effects described by a Hubbard-type on-site Coulomb
repulsion, not included in a density functional description [10]. The
inclusion of the DFT + U approach has critical importance in the
description of the SO2 adsorption on the α-Cr2 O3 (0001) surface. To
our knowledge, this is the first theoretical investigation of SO2
chemisorption on the α-Cr2 O3 (0001) surface.
The work methodology, which includes the experimental setup as
well as the theoretical approach, is presented in the next section. In
the following section the experimental and theoretical results are
reported and discussed and finally the conclusions are exposed.
2. Methodology
2.1. Experimental setup

2.1.1. Gas supply

⁎ Corresponding author. CCT-La Plata-CONICET, Instituto de Investigaciones Fisico-
químicas Teóricas y Aplicadas (INIFTA), Facultad de Ciencias Exactas, Universidad
Nacional de La Plata, Calle 64 y Diagonal 113, 1900 La Plata, Argentina.
E-mail address: eemola@inifta.unlp.edu.ar (E.E. Mola).
Sulfur dioxide at a concentration of 10 ppm was circulated inside
our equipment. Nitrogen was the carrier gas used; it was supplied by a
gas container with a gas meter to control the gas flow according to

0039-6028/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.susc.2010.12.004
490 V.A. Ranea et al. / Surface Science 605 (2011) 489–493
Fig. 1. Experimental setup. (A) Reactor, (B) Electrical Heated Oven, (C) Rotameters, (D) Sulfur Trap, (E) Bubbler with distiller water, (F) Bubbler with a dilute sodium hydroxide
solution, (G) Sulfur dioxide Concentration Register SafeLog 100, (H) Gas Cooler Device, (I) Partially narrowed column.
experimental requirements. A flow control valve and a rotameter
were used in order to ensure a nitrogen flow within the range
50–500 ml/min (C in Fig. 1). During the TPD experiments a flow of N2
was made to circulate with the flow control dose mentioned above.
2.1.2. Reactor
The experiments were performed in a fixed bed reactor (A in Fig. 1)
made of quartz and tubular shaped (column) 100 cm long and of
diameter 0.6 cm. The internal wall of the tube is partially narrowed
(along a distance of about 2 cm) around the middle column length to
support the stuff (fixed bed). The part of the column that is located
before the fixed bed works as a preheating zone for the incoming gases.
The column was placed in a vertical electrical oven (B in Fig. 1) of circular
section with upper and lower openings to remove the reactor in order to
clean it, to refill it and to place it again in the oven. The oven temperature
was adjustable up to 1200 ∘C by using an Iron-Constantan thermocouple.
The second zone is the area in which the column is partially narrowed
(I in Fig. 1). In that part of the column, and between two layers of quartz
wool, the alumina-supported chromium oxide (Cr2 O3 ) is placed.
2.1.3. Determination of SO2 concentration
Finally the gas that comes across the fixed bed flows through a
device that works as both a sulfur trap and a gas cooler (D and H in
Fig. 1). Then the gas flow comes across a SO2 concentration register.
This is an electrochemical cell SafeLog 100, Quest Technologies
capable of detecting down to less than 10 ppm of SO2 in the
outcoming gas mixture (G in Fig. 1). Then the gas mixture flow was
made to bubble firstly in an Erlenmeyer containing distilled water to
verify the presence of Sulfur Trioxide (SO3) (E in Fig. 1) and secondly
in another Erlenmeyer containing a diluted sodium hydroxide
(NaOH) in order to retain the remnant sulfur dioxide (SO2) and in
this way to avoid atmosphere contamination (F in Fig. 1).
2.1.4. Catalyst preparation
γ-alumina (catalyst support) was first dried overnight at 105 °C
and then burnt at 600 °C. Cr2 O3 was prepared in a precipitation glass
from an aqueous solution of Chromiun Nitrate Cr(NO3)3 9H2O, FLUKA
trade mark. The support, previously prepared, was then impregnated
in a rotastream with the Cr2 O3 . The amount of catalyst employed was
the amount necessary to produce a 10% w/w mixture with the
alumina. The rotastream used is a Buchi, Waterbath model B-480.
Water is evaporated at 70 °C under a pressure of 0.3 Bar. After
evaporation every sample was dried overnight in a stove at 105 °C
within a covered porcelain container. After that every sample was
burnt in a Carbolite furnace. A programmed rise temperature of 10 °C/
min is used until the temperature of 600 °C is reached, and then this
temperature is kept constant during 3 h.
2.2. Theoretical approach
2.2.1. Computational details
First-principles total energy calculations were performed using
DFT + U to investigate the adsorption of SO2 on the α-Cr2 O3 (0001)
surface as implemented in the Vienna Ab initio Simulation Package
(VASP) [12,13] code. The Kohn-Sham equations were solved using
projector augmented wave (PAW) method [14,15] and a plane-wave
basis set including plane waves up to 400 eV. Electron exchange and
correlation energies were calculated within the local spin density
approximation (LSDA) in the Perdew-Zunger form [16]. The DFT + U
method was used with values J = 1 and U = 5 [10]. Convergence is
considered achieved when the forces on the ions are less than 0.03 eV/Å.
Periodic boundary conditions are applied in the three perpendicular
directions. The Hessian matrix of second derivatives was determined for
ground structures within the harmonic approximation by two-sided
finite differences, using a displacement step of 0.01 Å. Adsorbed atoms
were displaced in the calculations, and diagonalization of the dynamic
matrix yields the harmonic frequencies.
The system is modelled by a hexagonal surface supercell with
lattice constants: a = 4.954 and c = 20 Å [17]. The surface is modelled
by a five-layer (Cr–O3–Cr) thick slab separated by 11 Å vacuum region
to avoid interactions between slabs. The nine external atomic layers
(Cr or O) were allowed to relax, together with the adsorbate, and the
six bottom ones were kept fixed at their ideal bulk positions. In the
calculation of the energy barrier for desorption, the SO2 molecule was
placed at different distances from the surface, the nine external
atomic layers and the molecular oxygen atoms were allowed to relax
freely, whereas the S was allowed to relax only in the xy plane at every
fixed z position. A (1 × 1) surface was used to investigate the SO2
adsorption for 1 ML coverage (one molecule per surface Cr atom). A
15 Å side cubic supercell was used to calculate the SO2 and SO23 −
energies, vibrational frequencies and structures. The first Brillouin
zone was sampled with a (3 × 3 × 1) Γ centered mesh and only the Γ
point was used for the cubic supercell.
 V.A. Ranea et al. / Surface Science 605 (2011) 489–493 491

The adsorption energy of SO2 is calculated as: similar relaxations [2,3,7,10,20,21]. The strong vertical relaxations are
due to the external Cr and O loss of coordination. Small lateral
Ea = EðSO2 = srf Þ−EðSO2 Þ−Eðsrf Þ relaxations of the O atoms of the second layer due to the deep inward
Cr relaxation are in agreement with previous results on alumina [20].
The first term is the energy of the optimized configuration of SO2
adsorbed on the clean relaxed surface. The second term is the gas 3.2. SO2 chemisorption
phase SO2 energy and the third term is the energy of the clean
optimized surface. With this definition, negative values of Ea are for SO2 adsorption was considered on many different initial config-
stable configurations. urations on the α-Cr2 O3 (0001) surface. The stable adsorption
geometries can be divided into two sets:
2.2.2. Conventional analysis of thermal desorption spectra
If the desorption experiment is carried out in a continuously • Chemi1, in this set the two oxygen atoms of the SO2 bind with two
pumped system with sufficiently high pumping speed, it can be different surface chromium atoms, and the sulfur atom is bound to
shown that the rate of desorption, − dθ/dt, is proportional to the one surface oxygen (Os).
increase in partial pressure of the desorbate. In practice, it is difficult • Chemi2, in this set one (two) oxygen atom(s) of the adsorbate is
to determine the constant of proportionality accurately. In the (are) bound to one (two different) surface chromium atom(s)
analysis given by Redhead [18] and Adams [19], it is assumed that without sulfur interaction with the surface.
the rate of desorption is given by a Polanyi–Wigner equation:
n
Although the geometries in the Chemi2 set are stable, they are not
−dθ = dt = νn θ expðEb = kb T Þ; ð1Þ the most stable ones, with a maximum chemisorption energy of Ea ≈
−2 eV. In this work we do not consider these adsorption configura-
where n is the reaction order, νn is the rate constant, and Eb is the tions because, they are probably local minima in the SO2 adsorption
energy barrier or activation energy for desorption from a single coordinate towards the final chemisorption state represented by
binding state. For a linear heating rate, T = T0 + β t, and assuming that Chemi1. This fact is confirmed by the TPD experimental results. No
νn and Eb are independent of coverage and temperature, it can be peak is observed at the corresponding temperature (Tp ≈ 450 °C) for
shown that: an adsorption energy of ≈ − 2 eV.
  Two adsorption configurations were found stable within the
2
Eb = kb Tp = ðν1 βÞ exp Eb = kb Tp f or n = 1; ð2Þ Chemi1 set. Their energies are: Ea = −3.09 and − 2.79 eV, named
site 4 and site 3, respectively. Fig. 2 depicts the SO2 chemisorption in
where Tp is the peak temperature in a plot of dθ/dt versus T, and ν1 is these configurations. Despite the fact that there are 0.3 eV between
equal to kbTp/h. their adsorption energies, the upper part of Table 2 indicates that
there are no structural differences between them around the
3. Results and discussions adsorbed molecule.
It also shows that in these adsorption geometries, the S–O bond
3.1. The α-Cr2 O3 (0001) surface lengths are ≈5% longer than in the SO2 gas phase geometry but they
are less than 1% longer than those in the SO23 − gas phase. The
The bulk α-Cr2 O3 can be described in terms of alternating formation of a S–Os (where the subscript s denotes an oxygen of the
chromium atom bilayers and oxygen atom layers in the [0001] surface) bond is reported with a bond length of 1.77 Å, which is 17%
direction. The O atoms structure corresponds to a slightly modified longer than the other two S–O distances and shorter than the ideal
hcp structure with Cr atoms occupying 2/3 of the octahedral sites. The Cr–O bond length, 2.02 Å (this bond is lost after the cleavage of the
ideal bulk spacing between O and Cr layers is 0.94 Å and between Cr surface). After adsorption, the O–S–O angle is smaller by 13° than the
layers is 0.38 Å [17]. This structure implies that there are only three calculated value in the gas phase (119°) but it is much closer to the
possible terminations of the (0001) surface: Cr–O3–Cr–, Cr–Cr–O3– value 112° calculated for the SO23 − gas phase. Similarly, the O–S–Os
and O3–Cr–Cr–. The chromium terminated (Cr–O3–Cr–) surface is the angles (100° and 94°) are much closer to the SO23 − O–S–O value.
most stable and will be the only one considered in this investigation. The inspection of the vibrational modes allows us to assign them to
This result is in agreement with previous results on the same surface the numerical results in the way exposed at the bottom of Table 2,
and on similar Metal2 O3 (0001) structures [2,3,7,10,20,21]. although some coupling among vibrational modes appears due to the
Table 1 shows there is a general agreement in considering that the presence of the surface. Upon adsorption, the SO2 stretching modes
clean α-Cr2O3 (0001) surface undergoes profound vertical relaxations underdo strong downward shifts, the asymmetric stretching mode
of the outermost layers. Similar Metal2O3 (0001) structures (spin about 300–350 cm− 1 and the symmetric stretching mode about 500
polarized, Metal = Fe and non spin polarized, Metal = Al) undergo cm− 1. On the other hand, there is an upward shift about 100 cm− 1 in
the bending mode after molecular adsorption. Table 2 shows that it
Table 1 would be possible to distinguish between the adsorption configura-
Calculated DFT + U (LSDA) (this work) interlayer spacings relaxations of the clean tions site 3 and site 4 for the final SO2 adsorption geometry based on
α-Cr2 O3 (0001) surface in relation to the bulk values, Cr−O = 0.94 and Cr−Cr = 0.38 Å.
the difference between asymmetric stretching vibrational frequencies
For comparison, experimental and theoretical results are included: calculated DFT
(LSDA and GGA) (this work), LEED and MD simulations [2]. in both sites. A similar trend occurs when the comparison is against
the SO23 − gas phase vibrational frequencies. The calculated bending
DFT + U LSDA GGA LEED [2] MD [2]
modes for SO2 and SO23 − are similar and so are the higher vibrational
Cr(1)–O(2) − 61 − 70 − 53 − 38 − 58 frequencies after molecular adsorption. Smaller differences are
O(2)–Cr(3) +6 +4 + 14 − 22 0 obtained when the stretching modes are compared. The symmetric
Cr(3)–Cr(4) − 44 − 48 − 70 − 25 − 36
stretching mode values of the site 3 and site 4 configurations are
Cr(4)–O(5) +9 +6 + 12 + 12 + 17
O(5)–Cr(6) −2 +6 + 12 smaller than the SO23 − symmetric stretching mode value by about 240
Cr(6)–Cr(7) +7 − 44 − 56 cm− 1. This is half of the value when compared against the SO2
Cr(7)–O(8) −2 +1 + 10 symmetric stretching mode. Similarly, the frequencies of the asym-
O(8)–Cr(9) −1 −8 −5
metric stretching modes of the site 3 and site 4 configurations are
Cr(9)–Cr(10) +3 −8 −5
slightly smaller than those for the SO23 −. The site 3 and site 4
492 V.A. Ranea et al. / Surface Science 605 (2011) 489–493

Fig. 2. SO2 chemisorption on α-Cr2 O3 (0001). The left panel shows a lateral view of the sulfite-like formation after SO2 adsorption with the formation of a longer S–Os bond (1.77 Å).
Center and right panels depict top views of the two adsorption geometries in the Chemi1 set. Center and right panels show that there is a chromium atom of the fourth and third layer
under the sulfur atom. We name these two configurations as site 4 and site 3, respectively. The adsorption energies are − 3.09 and − 2.79 eV respectively. The arrows in the center
and right panels indicate the Os bound to the sulfur atom and the oxygens of the SO2 are bound to the surface Cr marked with the number 1. The angle O–S–O is 106° and the Os–S–O
angles are 100° and 94°. The numbers in the center and right panels are to individualize the layer. Big orange spheres stand for S atoms; medium red and blue spheres Os and O,
respectively; and small light blue spheres Cr atoms.

vibrational frequencies are much nearer the SO23 − gas phase than the interaction of one of these with the S of the adsorbed SO2, this O is
SO2 gas phase. pulled out of the layer.
Following the above comparison for the structure and vibrational The results reported in Table 3 indicate that the SO2 adsorption in
frequencies of the site 3 and site 4 configurations against SO2 and SO23 − site 4 configuration decreases nearer the ideal bulk the profound
gas phase, and from the results shown in Table 2, it can be concluded relaxations produced after the cleavage of the surface, when
that, after adsorption, the SO2 loses identity and becomes a sulfite-like compared with the site 3 geometry. This is probably the reason why
specie on the surface. site 4 is 0.3 eV more stable than site 3.
We found structural differences between the two configurations An important point is that the Chemi1 geometries are only
Chemi1 in the external layers of the surface. A comparison is shown in predicted within the DFT + U framework. Neither GGA nor LSDA
Table 3, in which the clean surface relaxations are included. A general predict the sulfite-like species formation after SO2 adsorption on the
comparison between the vertical relaxations of the clean surface and α-Cr2 O3 (0001) surface. They only predict Chemi2 geometries with
the site 3 configuration indicates that the SO2 adsorption in this weaker interactions.
geometry does not move back the atomic layers toward the 0% Many initial configurations were tried for SO2 adsorption looking
relaxation, i.e., the ideal bulk spacings. A different trend shows the SO2 for stable sulfate-like species on the surface that include the S
adsorption in the site 4 geometry. Most of the atomic layers undergo interaction with two different Os. Different angles of the molecular
smaller relaxations (respect to the ideal bulk) than in the clean plane were tested respect to vertical and horizontal axes. No stable
surface, especially the external five spacings. We do not find a surface sulfate-like species on this surface was found after SO2 adsorption.
reconstrutcion after SO2 adsorption on the clean Cr-terminated
surface under these working conditions.
The most important characteristic is found in the relaxation of the 3.3. SO2 desorption
third spacing. This is formed by the second and third chromium layers,
i.e., the most external complete chromium bilayer. The vertical A well-defined maximum is observed around 870∘C in the TPD
spacing between them in the ideal bulk is 0.38 Å. After the cleavage spectrum of SO2 on polycrystalline Cr2 O3 shown in Fig. 3. The
of the (0001) surface, this spacing undergoes a strong inward temperature of the system was raised following T = T0 + β t, with a
relaxation of 44% to 0.22 Å. After adsorption of SO2, this vertical heating rate β = 0.12 °C/s from 100 to 1000 °C. In this range of
spacing is 0.21 and 0.33 Å for the two geometries within the Chemi1 temperatures only one peak of desorption is observed. In this series of
set, site 3 and site 4, respectively. In the first case there is little change TPD experiments, high SO2 coverage is used, near 1ML. The
in the Cr(3)–Cr(4) spacing in relation to the clean surface (right panel temperature of the peak seems to be almost independent of the
of Fig. 2), whereas in the second case this spacing is nearer the ideal coverage, under these conditions.
bulk spacing (15% inward relaxation) (depicted in the central panel of An estimation of the energy barrier, Eb, for SO2 desorption from
Fig. 2). polycrystalline Cr2 O3 is made using the Polanyi–Wigner equation,
The calculation of the two outermost spacings are relative to the Eq. (2). The calculated value is Eb = − 3.12 eV.
average of the vertical coordenates of the three O atoms of the second
layer within the (1 × 1) surface cell. Because of the attractive
Table 3
Calculated interlayer spacings relaxations of the clean α-Cr2 O3 (0001) surface, site 3 and
site 4 configurations, in relation to the bulk values, Cr−O = 0.94 and Cr−Cr= 0.38 Å.
Table 2
DFT + U optimized geometries and calculated vibrational frequencies of the gas phase Clean surface Site 3 Site 4
SO2, site 3 and site 4. For comparison, calculated values for SO23 − gas phase are also Cr(1)–O(2) − 61 − 11 − 11
shown in the last column. In parenthesis the S–Os distance and the O–S–Os angles. O(2)–Cr(3) +6 + 11 +1
Cr(3)–Cr(4) − 44 − 46 − 15
SO2 Site 3 Site 4 SO23 −
Cr(4)–O(5) +9 + 11 +3
S–O (Å) 1.44 1.51, 1.51 (1.77) 1.51, 1.51 (1.77) 1.50 O(5)–Cr(6) −2 −5 −4
O–S–O (∘) 119 106 (100, 94) 106 (100, 94) 112 Cr(6)–Cr(7) +7 − 22 − 17
Asymmetric str. (cm− 1) 1302 1002, 972 965, 938 1126, 1021 Cr(7)–O(8) −2 −6 +5
Symmetric str. (cm− 1) 1101 604 605 845 O(8)–Cr(9) −1 −1 0
Bending (cm− 1) 495 593 590 506 Cr(9)–Cr(10) +3 +3 +2
 V.A. Ranea et al. / Surface Science 605 (2011) 489–493
160
140
120
100
ppm
80
60
40
20
0 1
600 650 700 750 800 850 900 950 1000
C
Fig. 3. TPD experimental results. SO2 desorption from polycrystalline Cr2 O3 supported
on alumina. A constant flux of 10 ppm of SO2 in a 200 ml/min flux of N2 (as carrier gas)
was used. The temperature was raised following T = T0 + β t, with a heating rate
β = 0.12 °C/s from 100 to 1000 °C. The catalyst mass of Cr2 O3 used in this experiment
was 0.075 g which was supported on Al2 O3 . The vertical axis shows the SO2 (ppm) and
the horizontal axis the temperature of the sample in Celcius degrees.
Fig. 4 depicts the calculated relative energy as a function of the
distance of the SO2 molecule to the (0001) surface. It shows no
evidence of an energy barrier for adsorption, within the approach we
are using in this article. A null activation energy for SO2 adsorption
allow us to compare the DFT + U calculated adsorption energy, Ea =
−3.09 eV, with the energy barrier for desorption, Eb = − 3.12 eV,
obtained from the experimental TPD spectrum (Fig. 3) and the
Polanyi–Wigner equation (Eq. (2)). The very good agreement
between these values could be interpreted as a support of the
sulfite-like species formation on the polycrystalline Cr2 O3 surface
after SO2 adsorption.
4. Conclusions
Several stable adsorption configurations were found for SO2 on the
Cr2 O3 (0001) surface. In all the cases the interaction occurs via the O
atoms to surface Cr atoms. In the two most stable adsorption
geometries, the S atom bounds to one Os in a sulfite-like geometry.
The adsorption energies are −2.79 and − 3.09 eV for the named site 3
and site 4 configurations, respectively. The calculated SO2 structures
on the (0001) surface are very similar as well as the calculated
vibrational spectra. After inspection of the relaxation of the external
layers, a few differences between configurations were found. The
atomic surface relaxations after SO2 adsorption in the site 4 are
smaller than those in the site 3 configuration. They are nearer the ideal
bulk spacings. This is probably the cause why the site 4 adsorption
structure is 0.3 eV more stable than the site 3 structure.
The TPD spectra of SO2 desorption from polycrystalline Cr2 O3
exhibit a desorption peak at Tp ≈ 870 °C with a heating rate of
β ≈ 0.12 °C/s. The conventional analysis given by the Polanyi–Wigner
equation estimates the energy barrier for desorption, Eb, in − 3.12 eV.
This value is in good agreement with the calculated adsorption
energy, Ea, for the site 4 configuration; assuming that the SO2
adsorption is not an activated process. The agreement could be
493
-1
-1,5
Energy (eV)
-2
-2,5
-3
2 3 4
z(S) - z(Cr) (A)
Fig. 4. Energy vs relative vertical distance. The lowest energy is − 3.09 eV, which
corresponds to the optimal geometry for SO2 chemisorption on the α-Cr2 O3 (0001)
surface. To calculate the other energy points, the sulfur atom is restricted to move only
parallel to the surface at different vertical distances. The rest of the atoms are free to
move or fixed as in the previous calculations.
interpreted as a support of the sulfite-like species formation on the
polycrystalline Cr2 O3 surface after SO2 adsorption.
It is important to note that the sulfite-like geometry is only
predicted within the DFT + U framework. Neither GGA nor LSDA
predict its formation after SO2 adsorption on the α-Cr2 O3 (0001)
surface.
Despite great efforts, no stable sulfate-like species were found on
this surface after SO2 adsorption.
Acknowledgments
This work was supported by Consejo de Investigaciones Científicas
y Técnicas (CONICET), Agencia Nacional de Promoción Científica y
Tecnológica (ANPCyT) PICT 06 31995, Universidad Nacional de La
Plata and the Faculty of Chemistry and Engineering Fray Roger Bacon.
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