ARTICLE

pubs.acs.org/JPCC

Structural Defects in W-Doped TiO2 (101) Anatase Surface: Density

Functional Study
Antonio M. M
arquez,* Jos
e J. Plata, Yanaris Ortega, and Javier Fdez. Sanz
Departamento de Química Física, Universidad de Sevilla, Facultad de Química, 41012 Sevilla, Spain
bS Supporting Information
ABSTRACT: In this Article, the structural and electronic
properties of the W-doped anatase (101) surface are investi-
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gated by first-principles density functional theory calculations.

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Several surface and subsurface substitutional positions are

examined as well as the interaction of the W-dopant atoms
with structural defects: cation vacant sites and additional oxygen
atoms that are required to compensate the extra charge of the
W6+ cations. It is found that the preferred configurations are
those on which one W6+ cation and one Ti vacant site are first
cationic neighbors with simultaneous formation of a wolframyl
entity. The main mechanism of system stabilization is found to
be based on the formation of wolframyl species that result from
the close proximity, as first cationic neighbors of the W-dopant atom and the Ti vacant site. A second factor for system stabilization
seems to be the separation of W6+ cations to reduce the energetic cost of the structural distortions introduced by the doping process.
Results from molecular dynamics calculations indicate that W6+ cations have a 5 + 1 coordination with two W O distances at 1.8 to
2.0 and 2.5 to 2.6 Å. All of these structural results are used to understand the experimental information available for W Ti
nanostructured oxides. The modifications introduced in the electronic structure of the anatase (101) surface by the doping process
are discussed and rationalized. A comparative analysis of the density of states of doped and undoped slab models of this surface and a
Bader charge analysis will be used to understand the electronic redistribution that takes place around the impurity atoms.

1. INTRODUCTION examining its performance in the photocatalytic degradation of

Titanium dioxide (TiO2) is a material that has received
considerable attention in the literature over the years because
of its versatility and multitude of its applications in catalysis,
photocatalysis, solar cells, waste remediation, and biocompatible
materials.1 9 In particular, nanocrystalline TiO2 has been ex-
tensively studied because of its notable catalytic and photocata-
lytic activity. Various experimental approaches are used to scale
the TiO2 particle size down to the nanometer range, resulting in
an increased surface area that goes parallel with an enhancement
of the chemical and photochemical activity. Of the different
titania polymorphs, anatase appears to be the most important for
these applications because the majority of nanostructured mate-
rials displays this specific structure,10,11 with the (101) face
dominating >94% of the crystal surface.12 An obvious problem
hindering the photochemical applications of TiO2 is its poor
visible light response due to its wide band gap (∼3.2 eV on the
anatase polymorph). Different approaches have been pursued to
narrow this band gap and increase visible light absorption. One of
the most common methods is the introduction of impurities in
the TiO2 structure, either nonmetals or metals.13,14
Nanosized W-doped TiO2 photocatalysts have been synthe-
sized and characterized by a few research teams.15 18 Tian et al.16
have used a simple hydrothermal process for the synthesis and
evaluated the photocatalytic activity of the prepared material by
methyl orange. However, in their procedure, the W-dopant was
incorporated to only ∼4 mol %, and the limited effect of doping in
the photocatalytic activity of the solid was related to the surface
presence of W6+ acid centers. A more detailed account of the
structural and electronic effects of W doping into the anatase
structure of nanosized materials is the work of Fern
andez-García
et al.17,18 They have synthesized nanostructured Ti W mixed
metal oxides using a microemulsion preparation technique. The
structural and electronic properties of the materials resulting after
calcination were characterized by X-ray diffraction, Raman, EX-
AFS, XANES, and UV vis spectroscopies. From their data, these
authors concluded that no phase segregation appears up to a W
content of ∼20 atom %, with cation vacancies being the main
mechanism to achieve charge compensation in the nanostructured
mixed W Ti oxides. The Raman spectra data indicate the
presence of wolframyl species (WdO) that, however, were not
detected by EXAFS spectroscopy. Besides, two kinds of W O
distances, distinctive of the anatase-type structure, are detected,
indicating that some distortion of the anatase network is required
to accommodate the W cations. The analysis of the XANES and
Received: April 7, 2011
Revised: July 26, 2011
Published: July 26, 2011

r 2011 American Chemical Society 16970 dx.doi.org/10.1021/jp203223f | J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
UV vis results seems to conclude that electronically Ti and W are
in +4 and +6 oxidation states, respectively, although some variation
of the W d-population is detected. The second main feature
obtained from the UV vis data is a moderate (∼0.2 eV) reduction
in the band gap of these binary solids with respect to that of bare
anatase that is related to an enhanced photocatalytic activity upon
sunlight excitation in the gas-phase photo-oxidation of toluene.
These authors have also conducted some LDA-density functional
theory (DFT) calculations in bulk models of the anatase structure
considering that W dopants are located in Ti sites and that charge
compensation occurs exclusively by the presence of Ti cation
vacancies. These calculations offered an explanation for the band
gap reduction in terms of the presence of W 5d states at the low-
energy edge of the conduction band but failed to account for the
structure distortions experimentally observed and also did not
reproduce the presence of WdO entities detected in Raman
spectroscopy. Other theoretical studies have been focused on the
effect of titania W-doping on the catalytic (thermal) oxidation of
CO,19 electrical conductivity properties,20,21 and effects of N/W-
codoping22,23 in the electronic structure of bulk TiO2. However,
none of these works has investigated, to any extent, the structural
implications on the presence of Ti vacancies and WdO entities
evidenced by the experiment,18 and only one19 has taken into
account the presence of surface wolframyl species but in the (110)
surface of the rutile polymorph.
In the present work, we use DFT calculations to address the
issue of the interaction between the W-dopant and the structural
charge-compensating point defect structures: Ti-vacancies and
wolframyl species, experimentally manifested. In particular, we
focus on the anatase (101) surface because, as previously
indicated, anatase is the main structural polymorph found in
nanostructured TiO2 materials, and the (101) surface is the
thermodynamically most stable crystal face. Therefore, its struc-
ture is expected to play a fundamental role in any chemical or
photochemical process that may take place on it. Moreover, the
activity of anatase in photocatalytic reactions is found to be much
higher than that of the rutile polymorph (see, e.g., refs 10, 24, and
25 and references therein).
After briefly presenting the necessary computational details
about the models and the methodology used, we will start by
examining the energetics and geometries of surface defects on
W-doped anatase TiO2. Experimental facts, like the observation
by EXAFS spectroscopy of a single local arrangement around the
W-dopant, the formation of surface WdO species, and the
interaction among W-dopant atoms, Ti-vacant sites, and surface
wolframyl species will be discussed and rationalized. In a later
section, the implications on the electronic structure of these
materials and the electronic redistribution that take place around
the position of the impurity atom will be explored.
2. MODEL AND COMPUTATIONAL DETAILS
Periodic 3D calculations were carried out using the VASP 4.6
code26 28 with the projector-augmented wave method
(PAW).29,30 In these calculations, the energy was computed
using the generalized gradient approximation (GGA) of DFT
proposed by Perdew, Burke, and Ernzerhof (PBE),31 and the
electronic states were expanded using plane wave basis set with a
cutoff of 500 eV. Forces on the ions were calculated through the
Hellmann Feyman theorem, including the Harris Foulkes
correction to forces.32 This calculation of the force allows a
geometry optimization using the conjugated gradient scheme.
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Figure 1. One 2 supercell model of a TiO2 (101) anatase surface with
three O Ti O layers. Atom labeling for the substitutional W positions:
5s, pentacoordinated surface site; 6s, hexacoordinated surface site; 6u,
subsurface hexacoordinated (up) site; and 6d, hexacoordinated subsur-
face (down) site. Atom colors: Ti, gray; O, red.
Iterative relaxation of the atomic positions was stopped when the
forces on the atoms were <0.01 eV/Å.
The anatase bulk lattice parameters are taken from previous
work33 in which the same theoretical approximations of this work
were used. The resulting parameters are a = 3.789 Å and c = 9.486 Å,
which are within 0.2% of the experimental values (a = 3.782 Å
and c = 9.502 Å).34 The anatase (101) surface was modeled with
different surface supercells to simulate various dopant and defect
concentrations. The first model (model I, Figure 1) is a supercell
containing 72 atoms, of dimensions 1  2 in the [101] and [010]
directions, respectively. In the [101] direction, the slab was three
TiO2 trilayers thick (nine atomic layers), with a vacuum of 9 Å
separating the slab images. The second model (model II) is
obtained by doubling the previous one along the [101] direction.
Therefore, it is a 2  2 supercell three TiO2 trilayers thick.
According to their size, structural calculations were performed in
model-I-derived structures using a Monkhorst Pack set of 2 
2  1 k points, whereas a 1  2  1Monkhorst Pack set was used
for model-II-derived configurations. In all cases, the atoms in the
bottom layer were kept fixed to their bulk positions during
geometry optimizations to simulate the presence of the bulk
underneath. Density of states (DOS) calculations were performed
using a denser 4  4  2 Monkhorst Pack set of k points.
Substitutional W doping was modeled by replacing one or two
Ti per supercell with W atoms. This results in models having
either ∼8 or ∼4% dopant atom concentration: 4% when only
one W/Ti substitution in model I or two substitutions in model
II are considered and 8% when two W/Ti substitutions are
considered in model I. Further inclusion in these models of the
kind of defects experimentally observed: Ti vacancy (VTi) sites
and wolframyl (WdO) species result in slab models having
either Ti1 3xO2W2x or Ti1 xO2+xWx composition, respectively
(Figure 2). On the latter, an Oad is added per W dopant atom
included in the model to allow for the formation of a surface
wolframyl specie. In the former, a VTi site is created every two W
dopant atoms to compensate for the extra charge added in the
system by the W6+ cations. Relative energies are computed for
model structures corresponding to either Ti1 3xO2W2x or
Ti1 xO2+xWx composition with respect to the most stable
configuration of the same composition. Full optimization of
dx.doi.org/10.1021/jp203223f |J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
Figure 2. Supercell models of W-doped TiO2 (101) anatase surface
showing the defects introduced to achieve charge compensation: (a)
model with two W atoms incorporating a VTi site (light blue sphere) and
(b) model with one W atom and an extra O included. The models show
the most relevant bond distances (in angstroms). Top: side view.
Bottom: top view. Atom colors: Ti, gray; O, red; W, ochre.
the cell parameters in some representative doped model struc-
tures results in relative changes in cell volume similar in both sign
and magnitude to the experimental data (∼0.8 to 0.9%). Con-
sequently, the changes in the computed relative energies are
quite small, 0.03 eV in the biggest case. So, we have kept constant
the cell parameters in these calculations given the small influence
of the remaining stress in the relative energies.
Molecular dynamics (MD) calculations were performed on
the Born Oppenheimer surface in the canonical ensemble at a
given temperature (298 K) considering different dopant contents
and defects. The temperature was controlled through the Nos
e
thermostat35,36 implemented in VASP. The numerical integra-
tion was done using a time step set to 3 fs. The system was
equilibrated for 1 ps, followed by a 3 ps production run.
Histograms for both systems’ temperature and total energy
during the production run were extracted. (See the Supporting
Information.) The width of these histograms confirms that the
system was adequately equilibrated because the temperature of
the system is found to be 298 K ( 6% and the energy of the
system is found to be constant within (0.5 eV. Both values are
considered to be reasonable given the system’s size. These MD
calculations were performed at the Γ point of the Brillouin zone
as a larger 4  4  3 slab was considered, which results in a model
composed of 288 atoms (96 Ti and 192 O). For these calcula-
tions, concentrations of 4 and 8% of W dopant atoms and a
mixture of both defects (adsorbed oxygen and titanium
vacancies) are taken into account. From these MD runs, the
radial distribution function (rdf) of the W O pair and the
vibrational density of states of these systems were obtained and
analyzed. The vibrational spectrum of the system was obtained
by considering the Fourier transform of the velocity autocorrela-
tion function (VACF) from the MD data.37 All atoms in the
above-mentioned slab model are included in the VACF.
3. RESULTS AND DISCUSSION
3.1. Structure. Experimentally quite intrincated interactions
are found to exist in transition-metal doped TiO2 between
different types of defects: cation/anion vacancies and the
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Table 1. Relative Energies (ΔEr) and Shortest W O Dis-
tances in Ti1 xO2+xWx Models Organized According to the
Position of the W Dopant Atom
W site ΔEr/eV rW O/Å
5s 0.00 1.76 1.713, 1.772, 1.782
6s 0.92 1.52 1.790, 1.836, 1.850
6u 1.34 1.79 1.817, 1.860, 1.871
6d 1.54 1.78 1.796, 1.817, 1.823
Figure 3. Relative energies of Ti1 xO2+xWx configurations as a func-
tion of the W Oad distance labeled according to the position of the W
impurity.
presence of surface species. In particular, in W-doped TiO2, it
is quite clear that bulk charge neutrality is achieved by formation
of cation vacancies. However, surface WdO entities are also
well-characterized by the presence of a line at ∼970 cm 1 in the
Raman spectra of Ti W binary metal oxides.18 Thus, it is
insightful to start by examining the interaction between the
dopant atoms and additional Oad atoms, available to produce
surface wolframyl species. Table 1 summarizes the energetics of
Ti1 xO2+xWx configurations examined, organized according to
the position of the W impurity. The individual relative energies
are plotted in Figure 3 against the W Oad distance.
The computed relative energies suggest that without the
presence of VTi defects W atoms clearly prefer a superficial
pentacoordinated position, binding the Oad at a short 1.71 Å.
This distance is typical of a WdO double bond and is in close
agreement with the experimentally W O distance of 1.75 Å
deduced from Raman spectra information. Substitution of a
surface Ti6s by a W atom is moderately less stable (0.92 eV),
whereas all subsurface W/Ti substitutions examined show to be
quite unstable (1.34 to 1.78 eV per W/Ti substitution). It should
be noted that we have attempted to check the possibility of
introducing the charge compensation O anion as an interstitial
impurity. However, when the O atom was initially located near to
the W dopant, the resulting final configuration displayed the
formation on a surface WdO entity with no interstitial O anion.
If the interstitial O atom was initially located far from the W
impurity, then the resulting geometry was less stable, ∼2.5 eV
with respect to the reference configuration. The trends found can
be related to the distortions introduced in the TiO2 anatase
network by the introduction of the dopant. The W O distances
displayed on the same Table 1 show that the introduction of the
W-dopant implies a shortening of the cation anion distances
dx.doi.org/10.1021/jp203223f |J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
Figure 4. Relative energies of Ti1 3xO2W2x configurations (8% dopant
concentration) as a function of the W W distance and labeled accord-
ing to the positions (surface or subsurface) of the three defects
introduced (two W and one VTi) into the TiO2 structure. Key: m,
number of defects in surface layer; n, number of defects in subsurface
layer. Triangles: no formation of WdO. Circles: a WdO entity is
observed.
with respect to those characteristic of the bare anatase structure
(1.93 to 1.98 Å). This explains that in the absence of VTi defects
that may ease the deformations introduced by the W-dopant,
surface substitutional sites are preferred over subsurface ones
because they require lower anatase structure distortion.
EXAFS spectroscopy data suggest the exclusive presence of a
single local arrangement, where W-dopants have one VTi site in
their first coordination shell.18 To obtain a detailed understand-
ing of the interaction among W-dopants, VTi sites, and WdO
entities that may simultaneously coexist, we have performed
DFT calculations on Ti1 3xO2W2x models that introduce a VTi
every two W/Ti substitutions to achieve the necessary charge
compensation. We have not systematically explored all possible
distributions of W-dopants and VTi sites in our models because
the number of different configurations to examine was too large.
Instead, taking advantage of the energetic preference, previously
discussed, for the formation of WdO entities and the available
experimental information, we have concentrated our configura-
tional space search into distributions where at least one W-do-
pant and one VTi site are first cationic shell neighbors.
Figure 4 shows the relative energies of Ti1 3xO2W2x config-
urations at the 8 atom % W-dopant concentration tested. These
data and examination of the optimized structures obtained clearly
indicate that the preferred configurations are those on which one
of the W6+ cations and the VTi site are first cationic neighbors
with simultaneous formation of a WdO entity. This situation is
most easily achieved when the three defects are at the surface.
The presence of a VTi site near a bicoordinated O anion leaves
this atom in an undercoordinated situation, and stabilization is
achieved by formation of a surface wolframyl group. However,
formation of WdO entities is also possible even when the three
defects (the two W-dopants and the VTi) are at subsurface
positions. The mechanism of formation of the wolframyl is
similar to that previously discussed: the formation of the VTi
reduces the coordination of one tricoordinated O anion and
facilitates its capture by the nearby W6+ cation, although the
WdO species remains in close coordination to a nearby Ti
cation. Whereas the data presented in Figure 3 indicate that the
main driving force to system stabilization is the formation of
wolframyl species that result from the proximity as first cationic
neighbors of the W-dopant and the VTi, a secondary stabilization
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factor seems to be the separation of the W cations. On average,
structures with W W distances lower than 4.0 Å seems to be less
stable by ∼0.7 eV than structures in which the two W W
dopants are 4.5 to 5.5 Å apart. The reason behind this behavior is
that in the first group both W6+ cations are first cationic
neighbors, so the distortions introduced in the TiO2 network
are concentrated into a small volume. In the second group of
structures, on the contrary, whereas the two W6+ cations are still
first neighbors to the VTi site, they are second cationic neighbors,
so there is more room to accommodate the distortions intro-
duced by the doping process. Further separation of the two W
dopants will result in one of the two W atoms being separated
from the VTi site. However, data from Ti1 3xO2W2x models with
a 4 atom % W concentration (not shown) indicate that this
situation is less favorable by ∼1.0 eV with respect to configura-
tions where the two W dopants are first cationic neighbors to the
Ti vacant site. These trends can be related to experimental
findings that indicate a highly homogeneous W Ti mixed oxide
distribution where the coordination number of the W Ti shell is
roughly three, supporting those models where charge compensa-
tion is fundamentally achieved by the presence of cationic Ti
vacancies.
To obtain further understanding of the short-range structure of
W Ti mixed oxides, we have performed MD simulations on
larger 4  4  3 TiO2 slab models with anatase structure having 4
and 8% Ti atoms substituted by W atoms. The W atoms occupy
both surface and subsurface positions, and charge compensation
is achieved in these models by a mixture of both VTi and Oad
defects. From these MD calculations, we have obtained the rdf for
the W O pair that is displayed in Figure 5. The first feature in the
rdf is a band centered at ∼1.9 Å asymmetric toward shorter W O
distances. The asymmetry of this band can be interpreted in terms
of two differentiated distances in the first coordination shell of
W6+ cations: a shorter one at ∼1.7 Å and a longer one at 2.0 Å
(labeled A and B, respectively, in the same rdf diagram). These
features are associated, respectively, with double-bonded WdO
species and with single-bonded W O. (See the inset in Figure 5.)
A second and less intense feature appears in the rdf at W O
distances of ∼2.4 to 2.6 Å (labeled C in the rdf diagram)
associated with surface WdO entities that significantly displace
a subsurface O anion. Integration of the rdf (Figure 5) indicates
that W atoms have a 5 + 1 coordination with the 5 first O atoms
located at distances below 2.0 Å and the last one displaying a 2.2 to
2.6 Å W O distance. These results can help us to understand the
experimental EXAFS data18 that clearly show, for samples with W
content below 15 atom %, that the first coordination shell of the
W cations displays two well-differentiated distances at 1.81 to
1.83 Å and 2.54 to 2.61 Å with a predominance of 5 + 1 coordina-
tion. The shorter W O distances are associated with features A
and B in our rdf data. The longer W O distances should be
interpreted as contributions arising from surface WdO entities
that significantly displace the subsurface anions. This last feature
was not reproduced in previous LDA calculations in bulk models
with anatase structure that considered that the only relevant
charge compensation mechanism was the formation of VTi sites.18
The inclusion in our models of surface (and subsurface) WdO
entities thus proves to be quite relevant. In any case, it is clear that
these materials have a complex defect structure resulting from the
interaction of W-dopants, associated VTi sites, and surface addi-
tional O anions that certainly must be present in the charge
compensation scheme. The analysis of the MD data is completed
by the calculation of the vibrational spectra of those systems.
dx.doi.org/10.1021/jp203223f |J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
Figure 5. Radial distribution function for the W O pair (left) and integrated coordination number for the W atoms (right). Inset showing the local
structure around the W atom with its six (5 + 1) first neighbors labeled.
Figure 6. Computed vibrational spectra (150 1200 cm 1 region) for
the W-doped (101) anatase surface models (continuous line) and
simulated experimental Raman WdO band (dotted line, data taken
from ref 18).
In agreement with the experimental infrared (IR) spectrum of
anatase,38 our simulated vibrational spectra for the (101)
W-doped anatase surface (Figure 6) display a series of strong
absorptions in the 100 850 cm 1 range. Neither anatase nor
rutile TiO2 shows any IR or Raman absorption above ∼850 cm 1.
However, in our computed vibrational spectrum, a new feature
develops at ∼1000 cm 1 associated with the WdO stretch mode.
This data is in agreement with the experimental line at
∼970 cm 1 observed in the Raman spectrum of nanostructured
Ti W mixed metal oxides18 (Figure 6). In light of these results
and of the experimental data mentioned above, we can conclude
that the surface tungsten species detected experimentally is
definitely a surface wolframyl group.
3.1. Electronic Structure. It is well known that GGA-DFT
methods usually underestimate the band gap values due to
inherent deficiencies in the functional, mainly the insufficient
cancellation of the self-interaction energy.39 The use of hybrid
exchange-correlation functional allows us to overcome these
deficiencies, and some of them are known to provide a good
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ARTICLE
description of the electronic structure of defected semiconductor
oxides.40,41 However, their application is rather expensive when
associated with the use of a plane wave basis set, and the amount
of HF exchange included in the potential is an external input that
largely affects the final description.42,43 Alternatively, the so-
called DFT+U approaches correct some of the inadequacies of
pure GGA functionals by making use of a Hubbard-like term to
account for the strong on-site Coulomb interactions. However,
this approach suffers from the dependence of the results on the
value of U, de facto an empirical parameter that has to be
adjusted. Whereas there is some consensus in the literature on
a value of U for the Ti 3d states of ∼4.0 to 5.0 eV to be the most
adequate,44,45 the situation is not the same when one looks for
the value of U to be applied to the W 5d states. In the previous
work of Long and English23 on bulk W-doped TiO2, different U
values were applied to the W dopant atoms. Values of U e 2.0 eV
as well as a standard GGA approach were found to result in an
incorrect metallic ground state. Thus, a value of U = 3.0 eV was
finally selected as in this case, W-doped TiO2 exhibited the
correct semiconductor behavior. It is important to stress that
these calculations did not take into account the presence of Ti-
vacancies or wolframyl species or any other charge compensation
mechanism. As result, in their calculations, there is an excess of
electrons that may be responsible for the incorrect metallic
electronic structure found.
In any case, GGA-DFT methods are useful when their results
are critically used to understand trends and obtain qualitative
features on the electronic structure of semiconductor oxides. To
this end, we have examined the DOS of different W-doped
anatase surface models. In Figure 7, we report the computed total
DOS for the 4% W-doped Ti1 3xO2W2x model and, to establish
comparisons, we also illustrated the total DOS of the undoped
anatase surface obtained from a similar slab model. The atom
projected density of states (PDOS) for the 4% W-doped
Ti1 3xO2W2x model is reported in Figure 7. The DOS of the
W-doped and undoped surface models has been aligned to have
the same Fermi level reference. Similar plots have been obtained
dx.doi.org/10.1021/jp203223f |J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
Figure 7. Total (top) and atom-projected (bottom) density of states of
4% doped Ti1 3xO2W2x model and undoped TiO2 anatase (101)
surface models. The origin is at the Fermi level of both systems. The
inset shows the lower edge of the conduction band.
regardless of the W substitutional position and charge compen-
sation scheme considered. Therefore, the electronic structure of
the W-doped anatase TiO2 surface is found to be essentially
insensitive to the position and concentration of W dopant atoms.
By comparing these DOS, we can see two evident changes that
take place upon W doping the TiO2 anatase surface. The first one
is the occurrence, at the lower level energy edge of the valence
band of a series of states with mainly O 2p character but with a
nonnegligible contribution of the W 5d energy levels. (See
PDOS in Figure 7.) These features are associated with the O
atoms that are first neighbors of the W dopant (except the O
from the WdO, which appears in the middle of the valence
band), and the overlap of the O 2p and W 5d energy levels found
is indicative of some degree of covalency on the W O bond. The
second modification of the DOS that takes place upon W doping
the anatase surface is found at the lower edge of the conduction
band. (See the inset in Figure 7.) This feature (that is similar in all
W-doped surface models) is responsible for the ∼0.1 to 0.2 eV
lowering of the band gap found in W Ti mixed oxides and is
mainly associated with a decrease in energy of the lowest Ti 3d
levels on the conduction band, as can be deduced from the atom
projected DOS. (See Figure 5b.) Detailed inspection of the
atom-projected DOS shows that the majority of this contribution
comes from the Ti atoms that are closer to the W impurity.
These observations can be rationalized by examining the
results of a Bader charge analysis. Of course the results of this
charge distribution analysis cannot be taken as absolute electron
population values but are useful for comparative purposes. The
formally W6+ cation has an average charge of +4.46e , whereas
the Ti cations are found to have a Bader charge of +2.63e . The
charge found the W-dopant is consistent with a high degree of
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covalency also evidenced by the overlap of W 5d and O 2p levels
at the lower edge of the valence band. The large Bader charge
found for the W cation with respect to that of the Ti cations
implies that the high electric field generated by the W cation will
drain electron density from the nearest Ti O bonds (the O
atoms have a 1.42e Bader charge, whereas in the undoped
model, the average charge is 1.36e ), weakening these Ti O
bonds and lowering the position of the associated Ti 3d levels in
the conduction band.
4. CONCLUSIONS
In the present work, a systematic study of the interaction
between W-dopant atoms and structural point defects experi-
mentally evidenced in nanostructured TiO2 materials has been
carried out by means of plane-wave pseudopotential calculations.
We focus this study on the (101) anatase surface because this is
the main structural TiO2 polymorph found in these kind of
materials, and the (101) surface is the thermodynamically most
stable crystal face. Our calculations show that without the
presence of VTi defects, W atoms clearly prefer a superficial
pentacoordinated position, binding the extra O atom (added to
the model to compensate the charge of the W6+ cation) at a short
1.71 Å distance, typical of a WdO double bond, whereas all
subsurface W/Ti substitutions examined show to be less stable.
These findings are related to the distortions introduced by the
doping process into the anatase structure: in the absence of VTi
defects that may ease the deformations introduced by the
W-dopant, surface substitutional sites are clearly preferred be-
cause they require lower structural distortions. DFT calculations
on models that introduce a VTi site every two W/Ti substitutions
clearly indicate that the preferred configurations are those on
which one of the W6+ cations and the VTi site are first neighbors,
with simultaneous formation of a WdO entity. Whereas this
situation is most easily achieved when the three defects are at the
surface, it is also possible when the three defects are at subsurface
positions. The mechanism of formation is explained in terms of
the reduction of the coordination of one O atom by the presence
of the VTi and its posterior capture by the W-dopant, with
formation of the wolframyl group. Whereas it is found that the
main driving force to system stabilization is the formation of
wolframyl species, a secondary factor seems to be the separation
of the W6+ cations: if both W6+ cations are first cationic
neighbors, then the distortions introduced into the TiO2 net-
work are concentrated into a small volume; if both W6+ cations
are second cationic neighbors, then there is more room to
accommodate these distortions. The rdf for the W O pair
obtained from MD calculations in models where charge com-
pensation is achieved by a mixture of both VTi and Oad defects
shows a predominance of 5 + 1 coordination for W6+ cations,
with two W O distances at 1.8 to 2.0 and 2.5 to 2.6 Å, allowing
for a rationalization of experimental EXAFS data. Our MD data
calculations allow us to assign these longer W O distances to
WdO entities that significantly displace a nearby O anion. In its
turn, the formation of these WdO groups is the consequence of
the presence of a VTi site that reduces the coordination of one
tricoordinated O anion and facilitates its capture by the nearby
W6+ cation. The computed vibrational spectrum, obtained from
our MD simulation, displays a band at ∼1000 cm 1 associated
with the WdO stretch mode, in agreement with the experi-
mental Raman line at ∼970 cm 1. The combination of our
structural data, the computed vibrational spectrum, and the
dx.doi.org/10.1021/jp203223f |J. Phys. Chem. C 2011, 115, 16970–16976
The Journal of Physical Chemistry C
available experimental information definitely proves that the
tungsten surface species experimentally detected is a WdO
group. Comparisons of the DOS for doped and undoped
(101) anatase surface models allow us to understand the changes
that take place in the electronic structure of these materials upon
W-doping. First, at the lower edge of the valence band, a series of
levels associated with the O atoms that are first neighbors of the
W dopants but with a nonnegligible contribution of the W 5d
energy levels is found. The overlap of the O 2p and W 5d levels
found in these features is indicative of an important covalent
contribution to the bonding, confirmed by the results of a Bader
charge analysis. The second modification of the DOS is found on
the lower edge of the conduction band associated with a decrease
in energy of the lowest Ti 3d levels with a majority contribution
coming from the Ti atoms that are closer to the W impurity. This
feature is responsible of the ∼0.1 to 0.2 eV lowering of the band
gap found in W Ti mixed oxides and is found to be independent
of the dopant atom concentration, in agreement with the
experimental information.
’ ASSOCIATED CONTENT
bS Supporting Information. Histograms for both systems’
temperature and total energy during the MD productions runs.
This material is available free of charge via the Internet at http://
pubs.acs.org.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: marquez@us.es.
’ ACKNOWLEDGMENT
This work was funded by the Ministerio de Ciencia e
Innovaci
on (Spain, grants MAT2008-04918, CSD2008-0023)
and the Junta de Andalucía (P08-FQM-3661). Computational
resources were provided by the Centro Nacional de Super-
computaci
on-Barcelona Supercomputing Center (Spain) and
Centro Inform
atico Científico de Andalucía (CICA). We thank
Mr. Roger Nadler for providing us with the program to obtain the
vibrational spectra from the MD data.
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