Surface Science 604 (2010) 10291033

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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

A periodic DFT study of water and ammonia adsorption on anatase TiO2 (001) slab
Rezan Erdogan a, Olus Ozbek a,b, Isik Onal a,
a
Department of Chemical Engineering, Middle East Technical University, Ankara, 06531, Turkey
b
Chemical Engineering and Chemistry Department, Eindhoven Technical University, Netherlands

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

Article history: Water and ammonia adsorption mechanisms on anatase TiO2 (001) slab surface are investigated by means of
Received 8 December 2009 periodic DFT approach. Molecular and dissociative adsorption energies for water are calculated to be
Accepted 10 March 2010 15 kcal/mol and 32 kcal/mol, respectively. Similarly, molecular and dissociative adsorption energies of
Available online 17 March 2010
ammonia on the same surface are found as 25 kcal/mol and 20 kcal/mol. A reverse result in this order is
reached for the previous case of ONIOM cluster study ( 23 kcal/mol and 37 kcal/mol, respectively). The
Keywords:
DFT
vibration frequency values are computed for the optimized geometries of adsorbed water and ammonia
Anatase molecules on anatase TiO2 (001) slab surface and compared with the values reported in the literature.
Water 2010 Elsevier B.V. All rights reserved.
Ammonia adsorption

1. Introduction
TiO2 has been extensively studied for many years as a model metal
oxide with a wide range of applications in catalysis, photochemistry,
and electrochemistry [1]. Especially in catalysis, anatase phase of
titanium dioxide is used much more often as a support or as a catalyst
by itself [13]. It has been proposed by a number of researchers that
the minority (001) surface is more reactive and plays a key role in the
reactivity of anatase nanoparticles [47].
Since TiO2 exposed to air will always be covered by a water lm,
the presence of hydroxyl group can affect adsorption and reaction
processes and also might enhance or diminish adsorption of other
molecules such as CO, NH3, and O2 on the surface. NH3 adsorption on
anatase TiO2 can be important for industrial catalytic reactions such as
selective catalytic reduction (SCR) of NO [8] and photo-oxidation of
NH3 over TiO2 [9,10]. Since periodic DFT involves heavy computations
but it is also a more accurate method, it would be interesting and
valuable to compare its results with those of ONIOM DFT method
performed in the previous study [11].
There are some experimental studies with regard to the surface
properties and adsorption reactions of water and ammonia on TiO2-
anatase surfaces. In the experimental studies by Ramis et al. [12] and
Topse et al. [13] it was reported that vefold coordinated titanium
atoms (acting as Lewis acid sites) and surface oxygen atoms which have
Bronsted base properties as the catalytic active sites of TiO2. With regard
to the adsorption mechanism, the experimental studies [1416]
reported that water and ammonia are molecularly adsorbed on TiO2-
anatase surface. In a study by Srnak et al. [14], two states of water and
Corresponding author. Tel.: +90 312 210 2639; fax: +90 312 210 2600.
E-mail address: ional@metu.edu.tr (I. Onal).
two states of ammonia desorption values were observed and desorption
activation energies of water and ammonia adsorbed states are estimated
from vacuum TPD (temperature programmed desorption) studies as
11 and 18 kcal/mol and 14 and 27 kcal/mol, respectively.
Munuera et al. [15] reported a heat of desorption value for water
adsorption on TiO2-anatase as 12 kcal/mol. Sprinceana et al. [16]
carried out a calorimetric study and reported a differential heat of 31
to 36 kcal/mol for ammonia adsorption on anatase titania.
There are many theoretical studies about water adsorption
reactions and surface properties on anatase TiO2 (001) and almost
all of them [4,11,1723] reported that dissociative adsorption
mechanism is the favorable path for water adsorption on anatase
TiO2 (001) surface. Vittadini et al. [4] reported that for 0.25
monolayer, water is adsorbed dissociatively with an adsorption
energy 37 kcal/mol by use of PW:DFT-GGA and CarParrinello
calculations. By using periodic HartreeFock method, Fahmi and
Minot [17] reported that water adsorbs on the titanium atom and then
dissociates to give hydroxyl groups. Nair [18] determined molecular
and dissociative water adsorption energy values on anatase TiO2
(001) by means of MSINDO-CCM (semiempirical molecular orbital
methodcyclic cluster model) calculations as 19 and 33 kcal/mol,
respectively. In the study of Jug et al. [19], molecular and dissociative
water adsorption energies on anatase TiO2 (001) are calculated by
means of MSINDO (semiempirical molecular orbital) method as 24
and 50 kcal/mol, respectively. Arrouvel et al. [20] reported that
water is mainly dissociated and adsorption energy varies strongly
with increasing coverage from 39 to 24 kcal/mol. In agreement
with previous theoretical studies, Gong et al. [21] found that
dissociative adsorption is favored, with average adsorption energies
of 29, 26, and 27 kcal/mol per H2O at 1/6, 1/3, and 1/2 ML
coverages, respectively, by use of PW:DFT-GGA and CarParrinello
methods. In our research group, Onal et al. [22] and Erdogan and Onal

0039-6028/$ see front matter 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.susc.2010.03.016
1030 R. Erdogan et al. / Surface Science 604 (2010) 10291033
[11] performed two cluster studies with regard to the water and
ammonia adsorption on anatase TiO2 (001) surface. The rst study by
Onal et al. [22] was carried out on a relaxed (001) cluster, and it was
reported that non-activated dissociation of water takes place with an
exothermic relative energy difference of 54 kcal/mol calculated via
DFT-B3LYP/6-31G** method. In another similar study by Erdogan and
Onal [11] an ONIOM cluster was used, and it was reported that water
molecule dissociates on anatase TiO2 (001) surface by a non-activated
process with an exothermic relative energy difference of 58 kcal/mol
obtained by means of DFT/B3LYP/6-31G**-MM/UFF level calculations.
Wahab et al. [23] reported molecular and dissociative water
adsorption energy values on anatase TiO2 (001) as 18 and
25 kcal/mol, respectively by means of semiempirical MSINDO
method. It was stated that the dissociated form of water molecule
adsorption on anatase TiO2 surfaces is always more stabilized than the
molecular form.
Although the adsorption mechanisms of water on (001) anatase
TiO2 have been extensively reported both in experimental and
theoretical literature, there are only three theoretical studies
accessible in the literature [11,22,24] concerning NH3 adsorption on
the same surface. Two of these three works are our own research
[11,22] and were carried out using non-periodic clusters. In the cluster
study, Onal et al. [22] reported that on relaxed cluster surface
dissociation occurs with a slight activation barrier of 3.6 kcal/mol and
an adsorption energy value of 36 kcal/mol. In the ONIOM cluster
study by Erdogan and Onal [11], molecular and dissociative NH3
adsorption energy values were calculated as 23 kcal/mol and
37 kcal/mol, respectively. Calatayud et al. [24] determined a
molecular adsorption energy value of 19 kcal/mol by using periodic
calculations, however; they did not indicate a dissociation case.
The objective of the present study is to theoretically investigate
adsorption of H2O and NH3 on TiO2-anatase (001) surface by means of
a periodic slab model and density functional theory (DFT) approach.
2. Computational method and surface model
The calculations are carried out by means of VASP [25] code, which
uses periodic plane wave basis sets. The electronic interactions are
described with PAW [26,27], and GGA (PW91) [28,29]. Except for the
molecules and atoms in the gas phase, dipole corrections are included
for the asymmetric slab calculations, where the top sides of the slabs
are used. The cut-off energies and k-points (Monkhorst Pack) used
are; 500 eV and (3 3 1) for 4 layer p(2 2) anatase TiO2 (001) slab
(Fig. 1). All the results reported in this work are carried out by
optimizing the respective structures until the net force acting on the
Fig. 1. 4 layer p(2 2) TiO2 anatase (001) slab.
atoms is smaller than 0.01 eV/. The atoms and the molecules in the
gas phase are represented with the same level of precision by
surrounding the species with a vacuum layer of minimum 10 in all
directions.
Anatase TiO2 (001) surface slab (Fig. 1) is prepared by initially
optimizing the respective crystal and then cutting the crystal along
(001) plane and placing a 15 vacuum layer above. The optimization
of the bulk crystal is carried out to determine the optimal lattice
parameters, which are calculated as a = b = 3.822 , and c = 9.670 .
These values are in a good agreement with the experimentally
reported values, 3.785 and 9.514 [30]. The adsorption energy is
calculated for adsorbate on the clean surface as follows:
Eads = Eadsorbate=surface Eadsorbate + Esurface
where Eadsorbate is the energy of the isolated molecule (H2O or NH3) in
the vacuum. Esurface is the energy of a clean anatase (001) surface, and
Eadsorbate/surface is the total energy of the molecule adsorbed together
with the (001) anatase TiO2 surface. One side of the slab is occupied by
adsorbed molecules. The coverage of adsorbed molecules is taken as
= 0.25 with respect to surface Ti atoms.
Following the optimizations to equilibrium geometries as described
above, the vibrational frequencies of adsorbed surface species are also
calculated. This is done by calculating the Hessian matrix based on a
nite difference approach with a step size of 0.02 for the displacements
of the individual atoms along each Cartesian coordinate. During the
frequency calculations symmetry is excluded explicitly. The frequencies
of the unfrozen surface atoms (phonons) are also calculated, however
they are not reported herein.
3. Results and discussion
3.1. H2O adsorption on anatase TiO2 (001)
For the adsorption reaction studies of small molecules (H2O, NH3),
vefold coordinated titanium atoms and the surface oxygen atoms are
used as the catalytic active sites of TiO2 and illustrated in Fig. 2. By
using a slab model and a periodic DFT approach, water adsorption on
anatase TiO2 (001) surface is investigated. Molecular adsorption
energy is evaluated from total energy calculations as 15 kcal/mol.
Fig. 2 depicts the optimized geometry of molecular H2O adsorption on
anatase TiO2 (001) slab model. For the molecular adsorption
geometry, the distances between hydrogen and oxygen of water
molecule (HwOw) and oxygen of water molecule and vefold
coordinated titanium (OwTi) are computed as 0.972 , and 2.171 ,
respectively.
For the case of dissociative adsorption mechanism, it is observed
that water molecule is dissociated on (001) anatase TiO2 surface with
an exothermic relative energy difference of 32 kcal/mol. For the
optimized geometry of this reaction (see Fig. 3), the distances
between hydrogen and oxygen of water molecule (HleftOw),
hydrogen of water molecule and surface oxygen (HrightOs), and
oxygen of water molecule and vefold coordinated titanium (OwTi)
are computed as 0.971 , 0.982 , and 1.892 respectively.
Very similar results to those found by Vittadini et al. [4] are
reached concerning the coverage and the structure of the bonds for
dissociative adsorption. It is found that dissociative water adsorption
occurs at 0.25 coverage with bond length increasing between the
bridging oxygen and the Ti atom. This structure can be seen in Fig. 3.
A comparison of calculated water adsorption energy values on
(001) anatase TiO2 surface with the available theoretical and
experimental literature is given in Table 1.
A comparison of the computed vibration frequency values of
dissociatively adsorbed H2O on (001) anatase TiO2 surface with the
available experimental literature is given in Table 2. In Table 2, the
change of frequencies upon adsorption of water molecule is also
 R. Erdogan et al. / Surface Science 604 (2010) 10291033 1031

Fig. 2. Optimized geometry of molecular H2O adsorption on anatase TiO2 (001) slab
model. a) Perspective view and b) top view. Fig. 3. Optimized geometry of dissociative H2O adsorption on anatase TiO2 (001) slab
model. a) Perspective view and b) top view.

reported as compared with water molecule in the gas phase. As can be

seen from this table, stretching frequency value of 3767 cm 1 for
dissociative water adsorption have a certain shift when compared
with the water molecule in the gas phase (3847 cm 1). The calculated Table 1
stretching vibration value of 3767 cm 1 is also in the experimentally A comparison of the calculated H2O adsorption energies on perfect anatase TiO2 (001)
surface with the theoretical and experimental values in the literature.
predicted range (36003800 cm 1) reported by [31] and agrees well
with the experimental value of (3715 cm 1) where (001) anatase Authors and Method Adsorption energy, kcal/
surface was assumed [32]. references mol

Molecular Dissociative
3.2. NH3 adsorption on anatase TiO2 (001) Theoretical
Fahmi and Minot Periodic 14 29
The most interesting issue in this study are the results obtained for 1994 [17]
ammonia adsorption on anatase TiO2 (001) surface. Adsorption Vittadini et al. PW:DFT-GGA 1/2 ML 19 33
1998 [4] Car-Parrinello
energy for molecular ammonia on anatase TiO2 (001) slab model is 1/4 ML 37
computed from the total energy calculations as 25 kcal/mol. Nair 2004 [18] DFT 19 33
Optimized geometry of this reaction is illustrated in Fig. 4 and it is Jug et al. 2005 [19] MSINDO 24 50
found that ammonia is molecularly adsorbed on the surface having an Arrouvel et al. PW:DFT-GGA KS (2439)
2004 [20]
NTi distance of 2.26 .
Gong et al. PW:DFT-GGA 1/6 ML 29
For the dissociative mechanism of ammonia adsorption, the 2005 [21] Car-Parrinello
resultant energy calculation shows that ammonia molecule is 1/3 ML 26
dissociatively adsorbed on the surface with an exothermic relative 1/2 ML 27
energy difference of 20 kcal/mol. The optimized geometry of this Onal et al. DFT-B3LYP/6-31G** Relaxed 25 54
2006 [22] cluster
interaction including the bond lengths is given in Fig. 5. The distances Erdogan and Onal DFT/B3LYP/6-31G**- ONIOM 24 58
of NTi, NH, and OH are calculated as 1.918 , 1.017 , and 0.982 , 2009 [11] MD/UFF cluster
respectively. Wahab et al. MSINDO 18 25
As in the case of water, it is found that dissociative ammonia 2008 [23]
This study PW:DFT-GGA-PW91 1/4 ML 15 32
adsorption occurs at 0.25 coverage with bond length increasing
between the bridging oxygen and the Ti atom (see Fig. 5). This is the Experimental
analogous structure for the ammonia dissociative adsorption to what Srnak et al. TPD Anatase 11,
was found by Vittadini et al. [4] for water dissociative adsorption. 1992 [14] TiO2 18
As a result of the periodic DFT calculations in this study, it is found Munuera et al. TPD Anatase 12
1999 [15] TiO2
that molecular ammonia adsorption on anatase TiO2 (001) surface is
1032 R. Erdogan et al. / Surface Science 604 (2010) 10291033

Table 2
Vibrational frequencies (cm 1) of H2O molecule in gas phase, dissociatively adsorbed
on anatase TiO2 (001) surface and in experimental literature.

H2O in gas phase Dissociatively ads. H2O Experimental anatase TiO2

OH stret. 3847 3767 36003800a, 3715b

a
Morterra et al. [31].
b
Primet et al. [32].

an energetically slightly more favorable process than dissociative

adsorption (25 kcal/mol vs. 20 kcal/mol).
A comparison of the computed adsorption energy values for the
ammonia adsorption on the defect-free anatase TiO2 (001) surface with
the available literature is given in Table 3. Experimental TPD [14] and
XRD, BET [16] studies investigated NH3 adsorption on real TiO2
(anatase) catalyst surface and therefore the slight deviation is
reasonable in view of the fact that (001) surface is minority in anatase
as previously mentioned. However, molecular ammonia adsorption
energy value (25 kcal/mol) obtained from periodic DFT calculations
in this study is quite comparable to the results of our preceding relaxed
[22] and ONIOM [11] cluster studies (27 kcal/mol and 23 kcal/mol,
respectively). A signicant difference is found in the relative stability of
dissociative NH3 adsorption between this study (periodic DFT) and
previous cluster studies [11,22]. Dissociative ammonia adsorption
energy value (20 kcal/mol) obtained in this study deviates signi-
cantly from the results of the previous relaxed [22] and ONIOM [11]
cluster studies (36 kcal/mol and 37 kcal/mol, respectively). As part
of an analysis study, ONIOM cluster calculations are redone by using
PW91 functional in Gaussian 03 instead of B3LYP functional; and the

Fig. 5. Optimized geometry of dissociative NH3 adsorption on anatase TiO2 (001) slab
model. a) Perspective view and b) top view.

results give a very similar trend albeit with 3 kcal/mol higher adsorption
energy for calculations involving the same PW91 functional used in
periodic DFT calculations. This eliminates the possible effect of using a
different functional. The most probable reason for these deviations may
be related to differences between periodic DFT calculations and
calculations involving small clusters with edge effects.
A vibration frequency study for ammonia adsorption is also
performed and a comparison of the vibrational properties of
molecularly and dissociatively adsorbed NH3 molecule on the (001)
surface with available experimental data reported for anatase surfaces

Table 3
A comparison of the calculated NH3 adsorption energies on perfect anatase TiO2 (001)
surface with the theoretical and experimental values in the literature.

Authors and Method Adsorption energy, kcal/mol

references
Molecular Dissociative Act. barrier

Theoretical
Calatayud et al. PW:DFT-GGA KS 19
2004 [24]
Onal et al. Relaxed cluster 27 36 3.6
2006 [22] DFT/B3LYP/6-31G**
Erdogan and Onal ONIOM cluster 23 37 2.7
2009 [11] DFT/B3LYP/6-31G**-
MD/UFF
This study PW:DFT-GGA-PW91 25 20
1/4 ML

Experimental
Srnak et al. TPD Anatase 14, 27
1992 [14] TiO2
Sprinceana et al. XRD BET Anatase (3136)
Fig. 4. Optimized geometry of molecular NH3 adsorption on anatase TiO2 (001) slab
1999 [16] TiO2
model. a) Perspective view and b) top view.
 R. Erdogan et al. / Surface Science 604 (2010) 10291033
Table 4
Vibrational frequencies (cm 1) of NH3 molecule in gas phase, molecularly and
dissociatively adsorbed on anatase TiO2 (001) surface and in experimental literature.
NH3 in gas phase Molecularly ads. NH3 Dissociatively ads. NH3
asym HNH stret. 3527, 3528 3510, 3535 (3400c) 3581, 3613
sym HNH stret. 3405 3385 (3350c) 3463
asym HNH bend. 1622, 1623 1573, 1609
(1599a, 1600c)
sym HNH bend. 1007 1094
(1190a, 1225a, 1215b)
HNH scis. 1448 (1480c, 1540d)
Experimental values are in parentheses and particular surface of the TiO2 (anatase) has
not been reported.
a DFT calculations: a partial review, Theor. Chem. Acc. 117 (2007) 663671.
Amores et al. [33].
b [8] S. Soyer, A. Uzun, S. Senkan, I. Onal, A quantum chemical study of nitric oxide
Teramura et al. [34].
c
Schneider et al. [35].
d
Lietti et al. [36].
in general is given in Table 4. In this table, the change of frequencies
upon adsorption of ammonia molecule is also reported as compared
with ammonia molecule in the gas phase. As this table shows,
asymmetric stretching frequency data of 3510 cm 1, 3535 cm 1 and
a symmetric bending frequency value of 1094 cm 1 for molecular
ammonia adsorption have a certain reasonable shift when compared
with the ammonia molecule in the gas phase (3527 cm 1, 3528 cm 1
and 1007 cm 1). Similarly, for molecular ammonia adsorption
asymmetric bending (1573 cm 1 and 1609 cm 1) and symmetric
stretching vibration (3385 cm 1) data also exhibit a shift from the
single ammonia molecule values (1622 cm 1, 1623 cm 1 and
3405 cm 1). Although the experimental values of 1599 cm 1 [33],
1600 cm 1 [35], and 3350 cm 1 [35] are in agreement with the above
calculated values, other experimental values such as asymmetric
stretching frequency (3400 cm 1), symmetric bending frequency
(1190 cm 1) and asymmetric bending frequency (1599 cm 1, and
1600 cm 1) data deviate signicantly from the corresponding
calculated values. The deviations from the experimental studies
could be expected since the particular surface of the TiO2 (anatase) on
which NH3 adsorbed was not determined in this real catalyst surface,
and it is known that (001) surface is minority in anatase. For the
dissociative ammonia adsorption, a vibration frequency value
(1448 cm 1) of scissoring mode of NH2 species is approximately
comparable with the experimental value of 1480 cm 1 [35].
The frequency calculations also validate another important point
that equilibrium geometries have only positive frequencies.
4. Conclusions
The molecular and dissociative adsorption of water and ammonia
on anatase TiO2 (001) surface represented by a slab model are
investigated by use of periodic DFT calculations. DFT calculations
indicate that H2O molecule is dissociated on anatase TiO2 (001) slab
surface by a non-activated process with an exothermic relative energy
difference of 32 kcal/mol. The dissociated form of water on anatase
TiO2 (001) surface is energetically more favored than the molecular
form in accordance with other theoretical and experimental studies.
However, on the same surface it is found that molecular NH3
adsorption energetically may not be considered too different from
dissociative adsorption (25 kcal/mol vs. 20 kcal/mol).
Acknowledgments
This research was supported in part by TBTAK through TR-Grid
e-Infrastructure Project. TR-Grid systems are hosted by TBTAK
ULAKBM and Middle East Technical University. Visit http://www.
grid.org.tr for more information.
1033
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