Article

pubs.acs.org/JPCC

Presence of Gap States at Cu/TiO2 Anatase Surfaces: Consequences

for the Photocatalytic Activity
Nicola Seriani,*,† Carlos Pinilla,‡,§ and Yanier Crespo†,∥
†
The Abdus Salam International Centre for Theoretical Physics, Strada Costiera 11, 34151 Trieste, Italy
‡
University College London, London WC1E 6BT, England
§
Departamento de Fisica, Universidad del Norte, km 5 Via Puerto Colombia, Barranquilla, Colombia
∥
International Institute of Physics, Av. Odilon Gomes de Lima, 1722, Capim Macio, CEP 59078-400, Natal RN Brazil
*
S Supporting Information

ABSTRACT: Copper-modified titania is a system of interest for its potential for

photocatalytic applications in the production of solar fuels. Still, the role of copper in the
process is unclear. In this work, small copper clusters on the (101) and (100) surfaces of
anatase have been investigated by first-principles simulations based on density functional
theory, to shed light on their atomic and electronic structure, and to understand their effect
on the photocatalytic process. The main effects of copper on the electronic structure are to
provide states above the edge of the valence band of titania and to lead to the formation of
midgap states. There are two types of midgap states, respectively, associated with direct
Cu−Ti bonds and to Ti3+ polarons. The latter are the result of charge donation from
copper and lie in the vicinity of the surface. Moreover, the copper tetramer (Cu4) displays
empty states at the bottom of the conduction band that play a key role in accommodating
excess electrons. We discuss how these features should enhance the photoresponse of
TiO2, contribute to increase the lifetime of the photogenerated electron−hole pairs and
contribute to increase the activity of this material for CO2 reduction, a key step in the
photoproduction of hydrocarbons.

■ INTRODUCTION
Titania is the material of choice in photocatalytic applications
and has been the subject of intense scrutiny to understand the
mechanisms of the photocatalytic processes.1−13 Notwithstand-
ing its popularity, it still suffers from major drawbacks that
hinder its widespread use in commercial applications. These
disadvantages comprise a relatively large band gap, ∼3 eV, that
prevents photoabsorption in the visible range, and a low overall
efficiency of the photocatalytic process. For these reasons,
many attempts to enhance its properties through proper
catalyst modifications have been undertaken. Among these, the
addition of copper to titania has recently received considerable
attention, as this system is able to produce hydrocarbons from
carbon dioxide and water vapor under solar illumination.14−16
TiO2 nanotubes with copper particles led to the production of
carbon monoxide, hydrogen, and hydrocarbons.14−16 Hydrogen
production was also observed when copper particles were
embedded in nanostructured TiO2.17−20
Still, fundamental questions remain unanswered about the
mechanisms of photoabsorption, charge separation and trans-
fer, molecule adsorption, and reaction. In particular, the role of
copper in each of these steps remains to be elucidated, and such
understanding could lead to a more systematic improvement of
the catalyst’s properties. Regarding the effect of copper on
photoabsorption, the only experimental evidence regards
copper doping in titania, which has been shown to lead to a
decrease in the band gap of the material,21,22 but no equivalent
information is available for supported copper nanoparticles. On
the other side, the electrocatalytic conversion of CO2 to
hydrocarbons seems to be dependent on the particle shape and
surface morphology of copper catalysts.23 Such a dependence of
catalytic activities on particle shape is typically linked to the
surface chemistry of the catalyst. The oxidation state of copper
plays a role in the activity of the catalyst as well, with
nanocrystalline metallic copper being particularly active for the
electroreduction of CO.24 Also, Liu et al. investigated the effect
of different treatments during catalyst preparation for a Cu/
TiO2 photocatalyst for CO2 reduction, and found that a
reducing treatment gives the best activity.25 Moreover, a high
dispersion of the copper catalyst is important to achieve high
conversion rates.26 Regarding the mechanistic aspects of surface
chemistry of the Cu/TiO2 system, is is known that CO2
dissociates spontaneously on defective Cu(I)/TiO2 in the
dark.27 It was proposed that electrons, trapped at Ti3+−VO sites,
can migrate to CO2 resulting in a dissociative electron
attachment and in CO adsorbed to Cu+.27 This hypothesis
underlines the importance of the reduced state of the catalyst
and relies on the presence of trapped electrons in the vicinity of
Received: January 27, 2015
Revised: March 10, 2015
Published: March 10, 2015

© 2015 American Chemical Society 6696 DOI: 10.1021/acs.jpcc.5b00846

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the surface. These trapped electrons were not identified in the
experiments in the presence of copper. For pure titania it is
known that the reduced phase (TiO2−x) shows a Ti3+ state
located within the band gap.28−30 Regardless of whether the
Ti3+ state is related to an oxygen vacancy27 or a titanium
interstitial defect,31 it is generally accepted that it has an
essential role in enhancing the photocatalytic performance of
this material.31−34 However, whether copper has an effect on
the presence of Ti3+ sites remains an open question. Moreover,
it has been shown that metal nanoparticles enhance the charge
separation through the formation of a Schottky barrier, and
photogenerated electrons are transferred to the metal nano-
particles as their Fermi energy is typically lower than that of the
oxide.27,35 Whether this is true also for copper remains to be
seen. It is thus clear that a better characterization of the effects
of copper on the electronic structure of the system is necessary
and would contribute to shedding light on the overall
mechanism of the photocatalytic process and the specific role
of copper in it.
Given the many variables that can influence the activity of the
catayst (shape, oxidation state, mixing state with titania, ...) and
the many subprocesses involved in the photocatalytic reaction
(photoabsorption, charge separation and transfer, molecule
adsorption, chemical reactions, product desorption), it is
important to be able to consider different aspects of the
system one at a time, to disentangle the complex dependencies
of all these issues with one another. In this context, help can
come from computer simulations from first principles. In the
present work, we have investigated small copper clusters (1−4
atoms) on the (101) and (100) surfaces of anatase by density
functional theory (DFT) and DFT+U methods, to shed light
on the interaction between copper and titania and its effect on
the electronic structure of the system. It is indeed possible to
obtain atomically dispersed copper on titania surfaces.36−38 We
shed light on the interaction between copper and titania and its
effect on the electronic structure of the system. We find that
copper can induce both a shift in the bands of the material and
the appearance of midgap states, depending on its coordination.
Moreover, charge donated by the copper clusters to the TiO2
surface induces the formation of Ti 3+ species in its
neighborhood. We argue that the presence of the dipole
formed by the cluster and the Ti3+ species has an important role
in delaying the recombination of the photoinduced electron
and hole, where the hole is mainly attracted to the Ti3+ site,
while electrons get trapped in the Cu4 cluster.
In the next section, the computational methods are
described, then the results are presented and discussed. Finally,
a summary closes the article.
■
COMPUTATIONAL METHODS
Spin-polarized density functional theory (DFT) in the
generalized-gradient approximation (GGA) of Perdew, Burke,
and Ernzerhof (PBE)39 has been used throughout, also with the
addition of the Hubbard term (DFT+U).40 It is well-
known41−44 that simple DFT-based approaches fail to predict
the presence of the Ti3+ state in the electronic structure, due to
the self-interaction error inherent to the functionals used in the
local density and the generalized gradient approximations. To
correct this error, post-DFT methods like DFT+U and hybrid
functionals have been implemented.41−54 In fact, it has been
shown that DFT+U is able to improve the description of the
electronic structure of 3d transition metal oxides, including that
of localized Ti3+ defect states.30,42−44,46,53 All simulations were
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performed with the Quantum-Espresso code,55,56 employing
plane-wave expansion and Vanderbilt ultrasoft pseudopoten-
tials.57 Calculations were performed with the simplified version
of DFT+U by Dudarev et al.,58 as implemented in the
Quantum-Espresso code.59 The values of U have been taken
from the literature: a value of 4.2 eV was used for
titanium42,43,53 and of 5.2 eV for copper.60 Convergence of
the total energy, for bulk anatase, has been achieved using
cutoffs of 40 and 480 Ry for wave functions and charge density
respectively, and a grid of (4 × 4 × 2) k-points generated with
the method of Monkhorst and Pack.61 The (101) surface has
been modeled with a rectangular (1 × 2) surface cell of size
(10.27 Å × 7.57 Å), the (100) surface with a (2 × 1) surface
cell of size (7.57 Å × 9.55 Å). This ensures that the minimal
distance between clusters is at least of 5 Å, avoiding direct
binding between neighboring clusters. This corresponds to less
than 0.5 monolayers of copper on titania. Similar fractional
coverages were obtained also in experiments.36 The k-point
grids were chosen to have a k-point density similar to that
employed for the bulk. The TiO2 slabs have a thickness of ∼10
Å, and the vacuum between the TiO2 slab and its copy is ∼15 Å
thick. Clusters have been deposited on one side of the slab. We
have checked that this does not introduce any important
dipolar interaction with the copies: by increasing the vacuum by
20 bohr (corresponding to ∼10.6 Å), the surface energy
changes remain well below 1 meV/Å2. All atomic positions
were relaxed and atomic relaxations were performed until forces
were smaller than 10−3 a.u.
■ RESULTS AND DISCUSSION
Copper clusters deposited on two surfaces of anatase TiO2 have
been considered: (101) and (100). Anatase is the most active
titania phase for photocatalytic applications,62 and these are the
two surfaces with the lowest surface energies.63−66 For the sake
of brevity, in the main body of the article, we show the figures
relative to the (101) surface and we comment about the
differences between the two surfaces. The full figures for the
(100) surface are reported in the Supporting Information (SI).
Atomic structures of small copper clusters (with 1−4 atoms)
have been generated by taking several configurations used in
the literature for similar systems, that is, Pd on TiO2(101)67
and Ag on TiO2(100),68 and by fully relaxing them. This
approach is justified by the fact that we are considering small
clusters, of up to four atoms. In principle, extensive structure
search employing global optimization techniques such as
genetic algorithms can be used to find the lowest-energy
structures of clusters and surfaces.69,70 Still, for such small
clusters these techniques invariably yield simple planar or
pyramidal geometries.71,72 Of course, the complexity of the
geometries increases very quickly if one considers clusters
larger than those investigated in the present work.
Structural Properties. TiO2(101). The configurations of
the energetically most stable clusters on defect-free (101) are
shown in Figure 1. In Table 1 the adsorption energies of all the
clusters are reported, calculated as
ECu@slab − Eslab − N × ECu atom
Eads = −
NCu atoms (1)
where ECu@slab is the total energy of the system with the cluster
on the slab, Eslab is the total energy of the bare surface, and
ECu atom is the energy of an isolated copper atom, and NCu atoms
is the number of copper atoms in the cluster.
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Figure 1. Atomic structure of the stable clusters with 1−4 Cu atoms
on the defect-free surface of anatase TiO2(101). Blue balls: titanium;
red balls: oxygen; gray balls: copper.
Table 1. Adsorption Energies (Eads), Total Charge Donated
to the Surface (Qdon(|e|)) and Change in the Polarization of
the 6c-Ti+3 Atom (Δμ(μB)) Produced by Copper Clusters on
Anatase Surfaces (101) and (100), as Calculated with DFT
+U
Eads (eV/Cu) Qdon(|e|) Δμ(μB)
Cu (101)/(100) (101)/(100) (101)/(100)
1 2.30/2.83 0.66/0.69 0.98/0.97
2 2.08/2.55 0.26/1.34 0.01/0.96
3 2.48/2.57 0.73/0.73 0.97/0.95
4 2.34/2.55 0.76/1.27 0.95/0.98
A single copper adatom (Cu1) prefers to lie at a bridge
position between two surface oxygen atoms. In this
configuration, the distance of copper from the two neighboring
oxygen atoms is 1.88 Å and its distance to two Ti atoms is 3.04
Å. A similar bridge position was found to be the most stable for
the copper adatom also on the (110) surface of rutile.73 This
structure was also the most stable for palladium on anatase
TiO2(101).67
On the contrary, the case of the Cu dimer (Cu2) is different
from palladium. We suspect that this is due to the different
dimer length and stiffness for Pd and Cu: for palladium, lengths
of 2.63−2.86 Å were calculated, while copper displays lengths
in a much narrower range (2.28−2.31 Å). The most stable
structure, shown in Figure 1b, is the one that can better
accommodate this Cu−Cu length on the surface. The other
structures reported in Figure 6 of ref 67 lie some tenths of eV
higher in energy. In the stable dimer structure, the second atom
is bound only to the first Cu and to a five-coordinated Ti (5c-
Ti) atom at the surface, with a Cu−Ti distance of 2.59 Å. In
fact, the dimer is the least stable among the cluster sizes
considered (Cu1−4), probably because of the unfavorable
geometry of this second Cu atom.
The stiffness of the Cu−Cu bond is found also in the trimer
(Cu3), where the bond lengths are 2.31−2.34 Å. The stable
atomic configuration for the trimer has two Cu atoms building
a bridge between two surface oxygens, and the third is pointing
toward the vacuum (Figure 1c). The tetramer (Cu4) prefers the
compact coordination of a tetrahedron (pyramid), where each
Cu atom is bound to the other three. Here the distances are
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slightly elongated with respect to the smaller clusters (2.37−
2.38 Å). We calculated also planar geometries for the tetramer,
but they lie ∼0.5 eV higher. It is to be noticed that, in vacuum,
the planar geometry is the lowest-energy configuration;74 the
pyramid is thus stabilized by the surface. As in the case of the
Cu2 cluster, in the Cu4 there is a direct Cu−Ti bond, although
with a longer distance of 2.92 Å. As we will show later, this
bond will introduce changes in the electronic structure that
could play an important role in the photocatalytic activity of the
Cu/TiO2 compound.
TiO2(100). TiO2(100) has a higher surface energy as a
consequence of the higher number of dangling bonds present at
the surface. In the stable configuration of the Cu monomer, the
distance of copper to two oxygen atoms is 1.89 Å, and its
distance to two Ti atoms is 2.82 Å (see Figure 1a of the SI).
The Cu atom lies almost exactly along the internuclear O−O
axis, whereas silver lies at the center of a triangle formed by
three O atoms (see Figure 2a in ref 68). The difference is
probably due to the different size of the Cu and Ag ions: the
smaller Cu would be too far from the oxygen if put at the
center of the triangle, and therefore this configuration lies 0.2
eV higher in energy. The interaction with the surface is so
strong that the dimer is not stable, and the most convenient
configuration for two Cu atoms is one where each Cu atom lies
in a monomer configuration, sharing one oxygen with the other
Cu atom. In fact, as shown in Table 1, on (100) the monomer
is more stable than all other clusters considered. We take this as
a sign of the higher reactivity of this surface, as shown also by
the higher surface energy. The trimer prefers a triangular
configuration with one copper atom pointing toward the
vacuum and being coordinated only to the other two Cu atoms.
The triangular configuration is the same as that found on (101).
Also, the tetramer prefers to be in the tetrahedral geometry
(pyramid) as on (101), probably favored by the ideal
configuration of the surrounding oxygen atoms, such that
each of the three Cu atoms of the basis of the pyramid are
bound to the other three Cu atoms and to one oxygen atom
(1.82−1.84 Å; see Figure 1d of the SI). A flat tetramer parallel
to the surface lies 0.1 eV higher in energy, while flat tetramers
perpendicular to the surface, such as those shown in Figure 4 of
ref 68 lie at least 0.7 eV higher. In the stable trimer and
tetramer there is no direct Cu−Ti bond and the trimer is
slightly more stable than the tetramer on both surfaces.
Electronic Properties. TiO2(101). The atomic configura-
tion has important consequences for the electronic structure of
the system, showing differences between the results obtained
for the smaller clusters Cu1−3 and the Cu4 cluster, as shown in
Figure 2. The extension of the edge of the valence band (VB)
into the gap is mainly due to low-coordinated Cu atoms present
in the Cu1−3 clusters (Figure 2a−c). Here the 3d and 4 s states
of the copper atoms with coordination number smaller than 3
are those that contribute most to the top of the VB, extending it
by ∼0.7 eV into the band gap of titania. The higher the
coordination number is, the lower in energy the 3d and 4s
states; for example, there is a shift of ∼0.6 eV between the peak
of the 3d states of the three-coordinated Cu atom and the two-
coordinated Cu atom in the dimer (see Figure 2 of the SI).
This trend is confirmed in the tetramer where just a small
contribution, from the 3d states, to the edge of the VB is
observed (see Figure 3 of the SI).
A second important feature in the electronic structure is the
appearance of midgap states. There can be two types of such
states. The first state consists of Cu-4 s and Ti-3d orbitals, is
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Figure 2. Density of states of the stable clusters with 1−4 Cu atoms on the surface of anatase TiO2(101), calculated with DFT+U. Upper part of
each diagram: majority spin. Solid line: total DOS; red dashed line: Cu-3d states; green solid line with triangles: 4s states of the Cu atom with a Cu−
Ti bond; brown solid line with circles: Ti-3d states of a 6-fold coordinated Ti atom in the vicinity if the Cu cluster (see text); dark brown solid line
with diamonds: Ti-3d states of a 5-fold coordinated Ti atom with a direct Cu−Ti bond. The projections on the single states have been multiplied by
20 to put them on the same scale as the total DOS. The zero of energy has been set to the enegy of the lowest unoccupied orbital. We have chosen
to set the zero of energy to the energy of the lowest unoccupied orbital because this choice makes the electronic structure of different systems easier
to compare.

due to a direct Cu−Ti bond (Figure 2b,d), and is present both
in DFT and DFT+U. A second state is present only when the
system is relaxed with DFT+U, because it is due to polaron
formation at a six-coordinated Ti (6c-Ti) atom lying right
below the copper cluster. The important role of the Cu−Ti
bond in determining the presence of states in the gap is
confirmed by the analysis of the trimer on (100), where there is
no direct Cu−Ti bonding. As a consequence, the midgap state
due to this bond is absent (see Figure 2c). Midgap states due to
the presence of metal−Ti bonds have also been seen in the case
of Ag clusters.68 Below we will discuss how the roles of these
two midgap states for the dynamics of excess charges should be
different.
TiO2(100). The projected DOS of clusters on (100) shows
the same features as on (101) (see Figure 4 of the SI). The
main differences are related to the different atomic config-
urations with respect to (101). The shortest distance between
the Cu adatom and Ti atoms is 2.82 Å, much larger than the
Cu−Ti bond found in the dimer on (101), and there are O
atoms in between. As a consequence, the only midgap states are
observed for polarons on subsurface titanium ions. Since the
stable configuration with two copper atoms consists of two
separately adsorbed Cu atoms, each induces its own subsurface
polaron. Also for the tetramer, two polarons are found below
the copper cluster. In these two cases the charge donated to the
surface (Qdon) is larger (see Table 1).
Polaron State. Polaron formation has been observed for all
systems in both the (101) and the (100) surfaces, with the
exception of the dimer on the (101) surface. In all cases we
have characterized the polaron by the magnetic moment of the
Ti atom, its charge and by the geometric distortion. As
mentioned above, the polaron forms at a 6c-Ti atom lying right
below the copper cluster. Depending on the cluster size, the
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donated charge, Qdon, calculated using the Bader method,75,76 is
between +0.66|e| and +1.34|e| for systems with polarons (and
just 0.26|e| for the dimer on the (101) surface), as shown in
Table 1, resulting in a net positive charge present on the copper
cluster. Of the donated charge, only 0.2−0.3|e| is transferred to
the Ti atom where the polaron is sitting, while the rest is
delocalized on the oxygen atoms. This Ti atom is usually
indicated as a Ti3+ ion, but it is known that effective atomic
charges hardly ever reproduce the formal charges in transition
metal compounds (see ref 77 and references therein). This is
usually attributed to the idealized nature of formal oxidation
states and to the fact that electronic charge is anyway
delocalized over many atoms in the real material. Moreover,
effective atomic charges may be built according to different
principles, either from the total electronic charge distribution,
as in the case of Bader charges,75,76,78,79 or from the wave
functions, as in the case of Löwdin charges.80,81 In the latter
case, the actual values of the effective charges may depend on
the choice of basis set and atomic wave functions used for the
projection. This makes an assignment of charge to atoms not
univocal, and therefore the resulting values should be used with
care. To make the situation more compicated to analyze, the
electrons donated to these metal oxides go also to oxygen
atoms around the cation.82 Still, it is accepted in the literature
that a polaron in a transition metal oxide can be individuated by
an investigation of atomic effective charges, of the magnetic
moments and of the geometric distortion of the atomic
configuration. In particular, it has also been shown that in these
cases the spin localization, given by an increase in the atomic
magnetic moment, is a better indicator of the presence of the
Ti3+ ions than the effective charges.83−86 The change in
magnetic moment for the Ti atom in question is between 0.95
and 0.98 μB, as calculated through Löwdin analysis80 (see Table
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1). Bader and Löwdin analysis give similar results when
calculating the magnetic moment of an ion.86 The Ti−O
distances are also increased and amounts to 2.16 and 2.14 Å for
the azimuthal O atoms, and to 2.07, 2.18, 1.98, and 1.97 Å for
the basal O atoms (here we show data just for the Cu4 cluster
on (101)). For comparison, the other 6-fold coordinated Ti
atom under the Cu cluster has distances of 2.00 and 2.05
(azimuthal) and 1.89, 1.92, 2.03, and 2.05 Å (basal). The
polaronic state is visualized in real space in Figure 3a. This state
Figure 3. Isodensity surfaces for single midgap states for the system
with the tetramer on (101), as relaxed with DFT+U: (a) polaronic
state consisting mainly of t2g states of subsurface six-coordinated
titanium atoms (see text for a detailed description); (b) state
consisting mainly of s and p states of two of the copper atoms. These
states are those of the majority spin and are occupied.
is pushed down into the gap and is clearly visible in the DOS
(Figure 2d). Its position is over 1 eV below the edge of the CB,
close to the position of the F-centers created by oxygen
vacancies at the (110) surface of rutile, which experimentally lie
0.7−0.9 eV below the edge.53,87−89 We have checked the
possibility of polaron formation on other Ti ions, and found
that the polaron can exist as a metastable state in other
positions, with energy differences smaller than 0.2 eV in most
cases. We compare this with the situation of polarons induced
by VO in rutile (110) surface, where activations barriers were
∼0.1 eV,49 allowing for electron hopping at room temper-
ature.53 Therefore, we expect that at room temperature a
polaronic state will form in the 6c-Ti atom below the Cu
cluster, as shown in Figure 3a, and will remain in the near-
surface region. We think that this property is also important for
the enhancement of the photocatalytic performance of the Cu/
TiO2 system as argued below. As a final note, the existence of
such Ti3+ sites in the presence of copper clusters could be
tested by electron paramagnetic resonance.90
Consequences for the Photocatalytic Activity of Cu/
TiO2. We have shown that the effect of the Cu clusters on the
electronic structure of titania is 2-fold. First, Cu atoms with a
coordination number lower than three contribute to the
extension of the edge of the valence band (VB) into the gap.
Second, Cu clusters induce the appearance of midgap states of
two kinds: one state is due to the presence of a Cu−Ti bond,
while the other is a Ti3+ polaron state generated by the
localization of the charge coming from the copper on a 6c-Ti
atom right below the cluster. In pure titania, it has been
suggested that storage of electrons at Ti3+ sites determines the
photocatalytic activity,4,27,91 maybe by increasing the photo-
absorption.92 Indeed, it is known that polarons easily migrate to
the surface in titania, and that electrons from Ti3+ sites are
involved in dissociative electron attachment of CO2 even in the
dark.27 In pure titania, Ti3+ ions have been observed in
correspondence of oxygen vacancies (VO-Ti3+ sites).96 Our
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calculations support the view that copper can induce the
formation of further Ti3+ sites, beside those present near
oxygen vacancies. If it is true that Ti3+ sites play a decisive role
in fostering the photocatalytic activity, then one of the main
positive effects of copper could be that of increasing their
number in the vicinity of the surface.
We note however that there is a major difference in the
electronic structure between Cu clusters with less than four
atoms and the Cu4 cluster. The tetramer displays Cu empty
states right at the bottom of the conduction band, while these
states are absent for the other clusters. These states are
important because they are related to the dynamics of
photogenerated electrons. Indeed, metal nanoparticles on
TiO2 can typically trap photogenerated electrons and make
them available for reduction of adsorbed molecules.27,35 This is
not the case for clusters containing less than four atoms, as the
available free states of Cu are high in energy in the CB (Figure
2a−c). On the contrary, the Cu4 cluster shows a localized
empty state at the bottom of the CB, which is the minority spin
channel of the state shown in Figure 3b. This is a state where
photogenerated electrons can be trapped, in agreement with
what is usually expected for metal clusters at the surface of
titania, promoting charge separation and transfer to the
reactants.27,93 This situation is analogous to that encountered
at macroscopic metal−semiconductor interfaces, where a
Schottky barrier forms,35 retarding the recombination of a
e−−h+ pair and therefore increasing its lifetime.94,95
To investigate the fate of electrons and holes in this system,
we have considered the electronic structure of charged cells
with the copper tetramer on (101), a cell with one additional
electron and a cell with a hole (Figure 4). The excess electron
occupies the minority-spin state at the Cu−Ti bond (Figure
4a); this state is spatially similar to its majority-spin counterpart
depicted in Figure 3b and was the lowest lying unoccupied
Figure 4. Density of states for the charged cluster with four Cu atoms
system on the surface of anatase TiO2(101). Upper part of each
diagram: majority spin. (a) System with an excess electron; (b) System
with an excess hole. Here we have used the same lines and color codes
of Figure 2. The zero of energy has been set to the energy of the
lowest unoccupied orbital.
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orbital in the neutral system. The polaron state remains
unchanged. On the contrary, in the system with a hole, the Ti3+
polaron state disappears from the DOS, while the other features
remain unchanged (Figure 4b). Thus, these results support the
idea that a copper cluster at the surface of titania is very
important for charge separation, with holes migrating toward
Ti3+ polaron sites and electrons moving toward the copper
cluster. Additionally, the presence of Ti3+ near the Cu−Ti
interface could contribute to the creation of active sites for the
CO2 reduction near this interface, even in the dark. Indeed, in
pure reduced titania it was observed that Ti3+ sites lead to
dissociative electron attachment to CO2, with production of a
CO adsorbed to Cu+.27 This hypothesis will be addressed in
future studies.
■
CONCLUSIONS
In this work, the atomic and electronic structure of small
copper clusters (1−4 atoms) on the (101) and (100) surfaces
of anatase have been investigated by DFT and DFT+U. The
main conclusions are as follows:
(a) On the more stable (101), copper tends to form clusters;
on (100) the Cu-TiO2 interaction is stronger and, for
example, favors single adatoms over dimers.
(b) The effect of copper on the electronic structure is 2-fold:
first, Cu atoms with small coordination numbers, that is,
<3, provide states that extend the edge of the valence
band into the gap by as much as ∼0.7 eV, mainly through
their 3d states. Second, two kinds of midgap states
appear, due to (i) a Cu−Ti bond and (ii) the formation
of a polaronic Ti3+ state in the vicinity of the copper
cluster by charge donated by the cluster. We expect that
these features will enhance the photoresponse of the
TiO2 in the visible light spectrum.
(c) The formation of copper-induced Ti3+ states might be
the main contribution of copper to the enhancement of
the photocatalytic activity of titania.
(d) The electronic structure of the system with a Cu4 cluster
is different from those with smaller clusters. The Cu4
cluster has an empty state at the bottom of the
conduction band (CB) and this state becomes full
when an additional electron is added to the system. This
behavior is in agreement with the expectation that
photoexcited electrons are transferred from titania to
metal clusters at the surface. On the contrary, in clusters
with less than four atoms, the empty states are well above
the bottom of the CB, and therefore, it seems probable
that photoexcited electrons will not be transferred to the
cluster.
(e) A hole added to the system prefers to sit on the Ti3+
polaron site near the titania−copper interface, leading to
the disappearance of the polaron itself. Together with the
previous point, this suggests that copper actively
contributes to separate photogenerated electrons and
holes.
■
ASSOCIATED CONTENT
*
S Supporting Information
Supporting figures. This material is available free of charge via
the Internet at http://pubs.acs.org.
6701
Article
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: nseriani@ictp.it.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Computational resources were provided by CINECA under
IscrC-Copsol and by The Abdus Salam ICTP. Y.C.’s position
was partly sponsored by the “ERC Advanced Grant 320796 −
MODPHYSFRICT”.
■
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