Article

pubs.acs.org/JPCC

Self-Sensitized Photocatalytic Degradation of Colorless Organic

Pollutants Attached to Rutile NanorodsExperimental and
Theoretical DFT+D Studies
Kezhen Qi,† Filip Zasada,*,† Witold Piskorz,† Paulina Indyka,† Joanna Gryboś,† Mateusz Trochowski,†
Marta Buchalska,† Marcin Kobielusz,† Wojciech Macyk,*,† and Zbigniew Sojka†
†
Faculty of Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Kraków, Poland
*
S Supporting Information
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ABSTRACT: Utilization of visible light by photosensitization

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of semiconductor photocatalysts via surface attachment of

small colorless organic pollutants (COP) is an effective way to
stimulate their photocatalytic degradation. Herein, by means of
the spectroscopic, photoelectrochemical, spectroelectrochem-
ical, and photocatalytic studies combined with the DFT+D
molecular modeling, we show how disubstituted benzene
derivatives, like catechol (CAT), salicylic acid (SAL), phthalic
acid (PTA), and terephthalic acid (TPA), can tune the
photocatalytic properties of rutile nanorods with the dominant
(110) termination. We elucidated in a systematic way the COP
ligand-binding configurations, the alignment of energy levels, and the charge-transfer pathways from the organic admolecules to
the titania substrate. The pDOS structures of the COP@r-TiO2(110) assemblies were interpreted in terms of electronic
interactions between the titania photocatalyst and the COP adspecies. It was shown that the appearance of additional states
within the band gap and in the conduction band allows for a one-step HOMO → CB ligand to metal charge transfer and a two-
step HOMO → LUMO → CB sensitization. Screening of the photocatalytic performance of the COP@r-TiO2 samples revealed
that the self-degradation efficiency gauged by the initial rate constant varies in the following order: catechol (−OH, −OH; 0.024
min−1) > salicylate (−OH, −COOH; 0.013 min−1) > phthalates (−COOH, −COOH; 0.005 and 0.004 min−1 for PTA and TPA,
respectively), showing a beneficial role of hydroxyl functionalities at an early stage of degradation process. It was found that the
higher activity of the OH-bearing catechol and salicylate adspecies was associated with the direct HOMO → CB electron-transfer
pathway operating in the visible light. The two-step HOMO → LUMO → CB mechanism (requiring UV light) characteristic of
carboxyl-bearing functionalities, despite favorable energy level alignment and coupling, is less efficient due to low density of the
electronic states at the top of the conduction band, and low flux of the solar radiation in that energy region. The in situ diffuse
reflectance spectroscopic (DRS) measurements revealed that at early stages of the photocatalytic degradation the aromatic rings
of the COP moieties are readily photohydroxylated, fostering the visible light utilization via the HOMO → CB electron transfer
route. Such latent autocatalytic hydroxylation processes are relevant for photocatalytic degradation of those pollutants that
originally do not exhibit hydroxyl functionalities provided that a photogenerated hole is localized at the organic moiety.

■ INTRODUCTION
Wide-band-gap semiconductors, such as titania, are promising
materials for a wide range of applications in environmental
photocatalysis1−4 and energy conversion.5,6 Their importance
results from the unique electronic properties that depend
mostly on the favorable energies of the band gap edges. Yet, the
photoactivity of TiO2 is limited by its rather large intrinsic band
gap of ∼ 3.0 eV, making this oxide capable of absorbing the
ultraviolet light only. This fact lowers the efficiency of the solar
light harvesting and disfavors photocatalytic degradation of
pollutants such as volatile organic compounds (VOC) or water-
soluble organic compounds (WSOC). Band gap engineering
and appropriate sensitization by bulk doping7−9 and surface
functionalization10−13 are then the key issues for more effective
application of various titania polymorphs as the proficient
photocatalysts. Band gap modifications, resulting from either
tuning the valence and conduction edge levels or by
introducing the empty or occupied states within the band
gap, are of a primary importance in chemical systems that
utilize light for various photocatalytic purposes. Another astute
approach involves fabrication of appropriate heterostructures
that play a crucial role in the titania photocatalyst amelioration,
as it has been recently reviewed.14 The resultant variants of
band alignment at the interface include a type I scheme, where
the band energy levels of one material straddle those of the
other resulting in the transfer of both holes and electrons to the
Received: November 9, 2015
Revised: February 15, 2016
Published: February 16, 2016

© 2016 American Chemical Society 5442 DOI: 10.1021/acs.jpcc.5b10983

J. Phys. Chem. C 2016, 120, 5442−5456
The Journal of Physical Chemistry C
narrower band gap material. In the type II heterostructures, the
band energy levels are staggered (or broken−type III), making
the charge separation energetically more favorable.15
Functionalization of semiconductor surfaces with organic
dyes has attracted much attention because the ensuing hybrid
interfaces allow us to control more effectively not only the light
harvesting but also the electron injection from the photoexcited
dye LUMO state to the semiconductor conduction band and
the charge recombination as well.16,17 Despite the undeniable
progress made in this field recently, understanding the detailed
mechanism of those processes at the molecular level is still a
subject of extensive experimental and theoretical investiga-
tions.18 Typically, the efforts toward improving the sunlight-
induced activity are focused at increasing dye extinction
coefficient, shifting its absorption toward longer wavelengths
to improve the compatibility with the solar light and a better
energetic matching between the electron donor and acceptor
levels.
In contrast to organic dyes, which are intentionally designed
to exhibit good light-harvesting properties due to their high
extinction coefficient, small aromatic pollutants are usually
colorless. Their efficient photodegradation depends essentially
on a direct excitation of the photocatalyst (UV-light) or a self-
sensitization effect,19 made possible even in the visible region
by favorable band alignment and appropriate frontier orbital
coupling to the conduction band states of the photocatalyst.20
It has been argued that formation of surface charge-transfer
complexes plays a beneficial role in pushing the photocatalytic
degradation of colorless organic pollutants (COP) toward the
visible region.21 However, until now, this issue has been rather
scarcely studied.
Among various wide-band-gap semiconductor materials,
rutile TiO2 (r-TiO2) is a common substrate for the design of
tailored heterointerfaces.22−24 The main exposed (110) facet of
the r-TiO2 crystals is not only very stable but also an excellent
template with protruding dangling bonds apt for interacting
efficiently with organic compounds such as alcohols (e.g.,
methanol),25 phenols (e.g., 4-chlorophenol),26 or aromatic
diols (e.g., catechol).27,28 These organic molecules with
different functional groups were used to exploit the site-specific
adsorption chemistry of the r-TiO2(110) surface.29
The density functional theory (DFT) modeling has been
widely applied to explore the interactions between organic
admolecules and oxide surfaces.30−32 For instance, Selloni et al.
studied self-organization of catechol on rutile (110)29 and
anatase (101)26,33 using DFT calculations supported by STM
imaging. They found that the most energetically favorable
bonding takes place in a bridging fashion involving two
titanium atoms. DFT calculations with inclusion of dispersion
forces revealed, in turn, the key importance of the van der
Waals interactions for ordering aromatic admolecules on the
rutile surface.34,35 Calzolari et al. have used DFT calculations to
study sensitization of the ZnO (10−10) surface by adsorbed
catechol and found that the alignment of energy levels
originates from the simultaneous interplay between the
conjugation of the adsorbed molecule and the electron
donor/acceptor capability of the specific anchoring groups of
the adsorbed molecule.36 Thomas et al. have investigated by
means of DFT modeling p-aminobenzoic acid (pABA)
interaction with the anatase-TiO2(101) surface. The observed
red shift after pABA adsorption has been attributed to the
presence of the highest occupied molecular orbitals within the
TiO2 band gap region.37
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The interaction between small benzene derivatives and the
titania surface depends not only on the structure of the exposed
facets but also on the chemical nature of the functional groups
acting as anchoring moieties. Among them, hydroxyl (−OH)
and carboxyl (−COOH) groups belong to the most common
anchors.38 Herein, we combine photocurrent, spectroelectro-
chemical, and photodegradation measurements with DFT
modeling to study the self-sensitization of r-TiO2 nanorods
with selected simple COP benzene derivatives, such as catechol,
salicylic acid, phthalic acid, and terephthalic acid. These
molecules contain hydroxyl and carboxyl functionalities in
different positions of the aromatic ring, which are commonly
formed during oxidation of aromatic pollutants. The goal was
to elucidate the impact of the anchoring diversity imposed by
the −COOH and −OH groups on the electronic structure
modification of the rutile nanorod photocatalyst, alignment of
energy levels, and the photodegradation pathways of these
prototypical colorless pollutants.
■ EXPERIMENTAL SECTION
Sample Preparation and Characterization. Synthesis.
For synthesis of rutile nanorods, 0.2 mL butyl titanate (TBOT)
was dropped into 16 mL of hydrochloric acid solution
(composed of 4 mL of 36.5% HCl, 12 mL of water, and 2
mg of cetyltrimethylammonium bromide). Then the mixture
was transferred to a 20 mL Teflon-lined steel autoclave and
heated at 180 °C for 24 h. Then the autoclave was cooled to
room temperature. The resulting product was separated by
centrifugation, washed several times with absolute ethanol and
distilled water, and finally dried at 60 °C in air for 5 h. The
synthesized material was additionally calcined at 450 °C for 3 h
to produce a well-crystalline r-TiO2 material. The surface
modification of the rutile samples with organic molecules was
achieved by impregnation of r-TiO2 (50 mg) with 5 mL of the
0.1 mol·dm−3 of COP solution in methanol. Catechol (CAT),
salicylic acid (SAL), phthalic acid (PTA), and terephthalic acid
(TPA) were used as exemplary COP molecules for surface
modification. The suspension of TiO2 in the COP solution was
treated with ultrasound for 5 min and left overnight. Then the
powders were centrifuged, washed 3 times with water, and
dried in the oven at 50 °C.
Characterization of Materials. The phase composition of
the samples was verified by X-ray diffraction (XRD) (Rigaku
D/max 2500 V/PC, Cu Kα radiation, λ = 1.5406 Å). UV−vis
diffuse reflectance spectra of the synthesized materials were
recorded using PerkinElmer Lambda 12 spectrophotometer
equipped with an integrating sphere of 5 cm in diameter.
Raman spectra were recorded using a Renishaw, in Via
instrument, operating with the 785 nm excitation laser source.
Transmission electron microscopy (TEM) imaging was carried
out by means of a Tecnai Osiris microscope (FEI) operating at
200 kV. Prior to TEM analysis the samples were ultrasonically
dispersed in methanol on a holey carbon film supported on a
copper grid (400 mesh). The grid was dried for 45 min, and
then surface contaminations were removed by plasma-cleaning
(Solarus Gatan 950). The simulations of TEM images were
carried out using JEMS simulation package.39 According to the
experimental conditions of imaging, the Cs and Cc coefficients,
equal to 1.2 μm, were used. Two perpendicular families of
diffraction spots, located on the diffraction pattern 3.26 nm−1
and 3.02 nm−1 away from the central spot, were assigned to the
(001) and (01̅1) planes, respectively, revealing a [110]
orientation of the specimen. In order to determine the values
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of defocus (Δf) and the specimen thickness (t), a wide range of
possible settings, from 55 to 72 nm for Δf and 2÷20 nm for t,
was tested. Detailed conditions used for image simulations are
presented in Table S1 in Supporting Information (SI).
Photoelectrochemical Measurements. Photocurrents were
measured using a three-electrode setup. The electrolyte (0.1
mol·dm−3 KNO3) was purged with argon for at least 5 min
prior to and during the measurements. A platinum wire and
Ag/AgCl were used as the counter and reference electrodes,
respectively. A 150 W xenon lamp (XBO-150), equipped with a
water-cooled housing and an automatically controlled mono-
chromator (Instytut Fotonowy), was used as the light source.
The working electrodes (ITO-coated transparent foil of 60 Ω/
sq resistance, Sigma-Aldrich, with the casted and dried
material) were irradiated from the backside through the ITO
layer in order to minimize the influence of the film thickness on
the measured photocurrents. The measurements were con-
trolled with the electrochemical analyzer (Autolab,
PGSTAT302N).
Photocatalytic Decomposition of COP Molecules. The r-
TiO2 powder (4 mg) and COP (0.1 mg) were suspended in
0.01 mol·dm−3 NaOH solution (in order to capture the
evolving CO2 for further analysis) and placed in a quartz
cylindrical cuvette (5 cm dia., 1 cm optical path, 17 mL
volume). A 150 W XBO lamp equipped with the 10 cm water
filter (with 0.1 mol·dm−3 CuSO4 solution) was used as the light
source with the fluence of 50−60 mW cm−2. The reaction
progress was monitored by measurements of the total organic
carbon (TOC) decay (Shimadzu, TOC-V series). In order to
elucidate the mechanism of self-sensitized photodegradation,
the SAL@r-TiO2 photocatalyst was irradiated , and the changes
in its chemical state were followed by diffuse reflectance
spectroscopy. The recorded spectra were converted into the
Kubelka−Munk function. The powder samples of SAL@r-TiO2
were ground in an agate mortar with BaSO4 (1:50 wt. ratio)
and pressed into pellets of ca. 2 cm in diameter. The catalyst
pellets were irradiated with 150 W xenon lamp (XBO-150)
equipped with a NIR filter (0.1 mol dm−3 aqueous CuSO4
solution) and 420 nm cutoff filter. The DRS spectra were
collected every 10 min in the range of 250−800 nm by means
of a Shimadzu UV-3600 spectrophotometer, equipped with an
integrating sphere (15 cm diameter). BaSO4 was used as a
blank reference.
Spectroelectrochemical Measurements. The measurements
were carried out in a three-electrode cell (quartz cuvette), with
platinum wire and Ag/AgCl as auxiliary and reference
electrodes, respectively. The cuvette was placed in front of
the integrating sphere, facing the working electrode (platinum
plate with deposited r-TiO2) toward the light beam. The
potential control was provided by the electrochemical analyzer
(BioLogic SP-150) with the scan rate of 0.5 mV·s−1. Relative
reflectance changes were collected by PerkinElmer UV−vis
Lambda 12 spectrometer equipped with a 5 cm diameter
integrating sphere.
Computational Details. For all calculations, the DFT
theory implemented in the Vienna Ab initio Simulation Package
(VASP)40 was employed. We used a projector augmented plane
wave (PAW)41 method for describing electron−ion interactions
together with the PW91 GGA exchange−correlation functional
as parametrized by Perdrew et al.,42 which produce reliable
results in describing electronic structure of oxide systems like
titania.43−45 In accounting for the electron correlation effects
and the Coulomb on-site repulsion, for proper reproduction of
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the band gap, we employed the DFT+U approach46 with the
Hubbard parameter set to U = 3.0 eV for all Ti ions. For
modeling the interaction between the hydrocarbon admolecules
and the oxide substrate, a semiempirical dispersion term,
parametrized by Grimme,47 was added to the quantum-
mechanical energies and gradients (DFT+D).
A number of tests of the TiO2 bulk properties were initially
performed to verify the accuracy of the applied calculation
scheme (variation of the cutoff energy and the k-point set). The
standard Monkhorst−Pack48 grid (4 × 4 × 3 sampling mesh for
bulk calculations and 3 × 3 × 2 for slab calculations) with the
cutoff energy of 450 eV and the Methfessel−Paxton49 smearing
parameter σ = 0.1 eV were used. For solving the Kohn−Sham
equations, the SCF convergence criterion was set to energy
change of 10−5 eV between two successive iterations. Geometry
optimization was performed until the changes in the forces
acting upon the ions were smaller than 0.001 eV/Å per atom.
Bulk titania unit cell was obtained by optimization of the
experimental tetragonal (D4h14-P42/mnm) rutile (2 × 2 × 4)
unit cell (a = b = 9.16 Å, and c = 11.80 Å) containing 96 ions
(Ti32O64). The optimal cell volume was calculated from the E/
V fit (Birch−Murnaghan equation of state50) with full
optimization of all internal degrees of freedom (with an error
<10−4 eV).
Initial surface geometry was constructed by cleaving the
optimized rutile structure in the [110] direction. For the
calculations, we used a (4 × 2) slab supercell (a = 12.17 Å, b =
13.36 Å), which consisted of 9 atomic layers with the thickness
of 9.01 Å and a vacuum layer of 20 Å, located above the
modeled surface in the [110] direction. Both the stoichiometry
of the bulk TiO2 (Ti48O96), as well as the top and the bottom
slab terminations, was preserved. The four outermost atomic
layers were allowed to relax, whereas the remaining deeper
layers were kept fixed at the optimized atomic bulk positions,
see Figure S1 and Table S2 in SI. In the aqueous environment,
the surface dangling bonds will be obviously replaced by the
hydroxyl groups; their influence on electronic structure,
however, should be of minor importance, so they are not
taken into account. Due to their high electronic hardness, the
hydroxyls should contribute to the DOS regions far from the
band gap region; therefore, for calculation of relative values,
their contribution cancels out to the large extend.
Adsorption of the COP molecules was performed with the
assumption that only one molecule per slab unit cell is present,
which gives the theoretical surface coverage of Θ = 0.61
molecule per square nm. This value is in accordance with
experimental assessment of the Θ value (vide inf ra) and
corresponds to the intermolecular distance between the
periodically repeated admolecules of at least 7 Å in each
direction. The adsorption energy (ΔEads) was defined as ΔEads
= ECOP@slab − (Eslab + ECOP), where ECOP@slab is the energy of
the optimized model of the COP/TiO2 assemble, Eslab denotes
the energy of the bare surface, and ECOP stands for the energy
of the isolated organic molecule. The atomic charges were
calculated using the Bader population analysis,51 and the bond
orders within the crystal orbital overlap population (COOP)
approach.
To estimate the injection time between the COP adspecies
and the semiconductor surface, the Newns−Anderson52 model
with the formulation of Persson et al.53,54 was employed.
According to this approximation, the effect of adsorption on the
electronic structure of the sensitizer is characterized by the
energy shift, relative to the dye level, and the level broadening
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(Γ), which provides a reasonable assessment of the lifetime of
the excited state, τ = 1/Γ. The level broadening was estimated
as the width of the fitted Lorentzian distribution of the density
of states. The partial DOS (pDOS) was calculated and
projected as a fraction of the total DOS (tDOS) to obtain
the dye’s contribution (rDOS). The projection coefficients, pi,
of rDOS are defined as follows:53,54
A plane (see below), shown in Figure 1c1 (Ti − blue, O − red),
∑ j (cijA )2
n
∑ j (cij)2
where i iterates bands and j iterates basis functions of dye
atoms A. The rDOS was then fitted to the Lorentzian
distributions by means of the Levenberg−Marquardt opti-
mization algorithm.55 The values of full width at half-maximum
(fwhm) of the obtained Lorentzians were used as input for the
Newns−Anderson model.
■ RESULTS AND DISCUSSION
Sample Characteristics. The XRD pattern and Raman
spectra (see SI, Figure S2) confirmed a high quality and phase
purity of the synthesized rutile (P42/mnm) samples. The results
of microscopic HR-TEM and electron diffraction characteristics
of the samples are presented in Figure 1. As revealed by Figure
Figure 1. High-resolution microscopic analysis of r-TiO2 nanorods. A
general view of the nanorods morphology (a1) together with
corresponding experimental and theoretical diffraction patterns (a2
and a3, respectively). Pristine (b1) and filtered HR-TEM images of the
r-TiO2 structure (b2) with the FFT pattern (inset) viewed along the
[110] direction. The simulated TEM images with the imposed atomic
structure (c1 Ti; blue, O: red) without (c2) and with the white noise
inclusion (c3).
1a1, the r-TiO2 photocatalyst consists of well-developed single
crystal nanorods of high aspect ratio ∼100 nm × ∼10 nm, and
the estimated thickness of 10−15 nm. The [110] orientation of
the nanorod was determined by the analysis of the
corresponding electron diffraction pattern (Figure 1a2). The
observed pattern is fully consistent with the simulated
diffraction for the P42/mnm structure using both the kine-
matical (green dots) and dynamical (red dots) approaches,
confirming definitely the rutile phase identity and the single-
crystal nature of the synthesized nanorods at the nanoscale
(Figure 1a3). The high-resolution TEM image of the r-TiO2
nanorod oriented along the [110] zone axis (obtained within
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the near Scherzer focus conditions) together with the pristine
and FFT filtered images are shown in Figure 1b1 and 1b2. The
indicated interplanar distances, d(001) = 3.056 Å and d(1−10) =
3.305 Å, corresponding to the (001) and (1−10) planes,
respectively, are in a very good agreement with the values
reported in literature.56
The DFT-optimized atomic structure of the rutile (110)
was used for simulation of the observed TEM pictures. The
resultant simulated images without noise and with inclusion of
the 40% noise (to match better the experimental conditions)
are shown in Figure 1c2 and 1c3, respectively. They match the
experiment very well. It should be noted, however, that there is
no simple, one-to-one correspondence between the observed
TEM spots and the atomic structure (cf. Figure 1c1 with b1 and
c3). In the applied TEM imaging conditions, the bright spots
are equivalent to the projected atomic columns, composed of
the Ti cations only, which are located at the corners of the
rectangular unit cell (shown in yellow in Figure 1c1, c2, and b1),
and separated by the d(100) and d(1−10) distances. The Ti
columns located at the edges of the unit cell and separated by
half of the d(001) period remain together with the O2− anions
practically invisible. The resultant characteristic pattern with the
4-fold symmetry, consistent with the inserted FFT image, is
then well reproduced in the simulated images.
The rutile nanorods functionalized with catechol [o-
Ph(OH)2], salicylic [o-Ph(OH)(COOH)], phthalic [o-Ph-
(COOH)2], and terephthalic [p-Ph(COOH)2] acids of differ-
ent −OH/−COOH ratio were next examined by IR spectros-
copy. The presence of the COP admolecules on the r-TiO2
nanorods was confirmed by appearance of their diagnostic
vibrational bands (see Figure S3 in SI). The surface loading in
the range of 0.12 to 0.57 molecules·nm−2 was estimated from
the amount of CO2 produced upon the temperature-
programmed oxidation of the samples, complemented by
BET surface measurements (Table S3, SI). These results were
used to build up the corresponding computational models.
Electronic Structure and Photocatalytic Activity
Studies. Following the literature,57 dye-sensitized TiO2
photocatalysts can be categorized into class-A and class-B. In
the case of the class-A systems, the electrons are injected from
the photoexcited dye admolecules to the titania substrate in a
two-step process (Scheme 1). For the class-B photocatalysts,
electrons are injected not only along the pathway A but also by
a direct one-step electron injection process via photoexcitation
Scheme 1. Mechanistic Pathways of Photoinduced Charge-
Transfer Processes in the COP@TiO2 Assembliesa
a
Class A: HOMO → LUMO → CB (left); class B: HOMO → CB
(right).
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of the dye-to-TiO2 charge-transfer bands. As a result, the nature
of the anchoring group as well as the energy positioning, shape,
and symmetry of the HOMO and LUMO orbitals of the
organic molecules to be photodecomposed play an important
role in their efficient self-sensitization. As discussed else-
where,58 an anchor that connects the admolecule to the catalyst
surface should exhibit a weak coupling of HOMO to the titania
CB manifold to prevent the charge recombination, yet strong
coupling of LUMO to foster the photoelectron injection rate.
Such a situation is preferred when LUMO is extensively mixed
with CB, whereas the HOMO orbital with possibly negligible
orbital density on the linking groups is left unchanged (class A).
On the other hand, a strong interaction of HOMO with CB
gives rise to efficient sensitization of the titania photocatalyst
owing to the development of a pronounced charge-transfer
band in the visible region (class B).
For a preliminary insight into electronic and charge-transfer
properties of the investigated COP molecules, we explored
briefly their molecular structure in the parent states. The energy
level manifolds and the shapes of the frontier orbitals for the
catechol, salicylic, phthalic, and terephthalic molecules are
shown in Figure S4, whereas their ionization potentials (IP),
electron affinities (EA), and the HOMO−LUMO energy gaps
(Eg) are collated in Table S4 in SI. The potential relevance of
these parameters for sensitization of titania is also discussed
therein. In the next step, we calculated electronic structure of
the COP@TiO2 assemblies in a distal and a proximal
configuration. For DFT calculations, it was assumed that a
single organic admolecule occupies the r-TiO2(110)(4 × 2)
slab, which corresponds to the coverage of 0.61 admolecule/
nm2, in line with the experimental estimate of the surface COP
loading (cf. SI, Table S3). For such coverage, the periodically
repeated molecules are mutually separated by at least 7.5 Å for
the top-on CAT, SAL, PTA adspecies, and by 6.1 Å in the case
of the plane-on adsorbed TPA molecules. In such arrangements
the calculated dispersion energies of the interaction of a given
admolecule with its four nearest neighbors were equal to 0.05,
0.04, 0.06, and 0.02 eV only, for CAT, SAL, PTA, and TPA,
respectively. Following previous literature,59 all calculations
were performed within an undefected titania surface model.
Several starting adsorption geometries of the organic molecules
placed on the TiO2(110) slab were explored. They include a
plane-on (horizontal) and top-on (vertical) attachment, a
mono- or bidentate bonding to the surface, as well as several
dissociative and nondissociative adsorption modes (see SI,
Table S5 and Figure S5 for more details). Only those with the
highest adsorption energies were subjected to further analysis,
and the obtained results are summarized in Table 1 and in
Figure 2.
Catechol Adsorption. The most stable adsorption mode of
this molecule (Eads = −2.90 eV with the dispersion part equal to
−0.43 eV) is a top-on conformation entailing deprotonation of
Table 1. Principal Adsorption Parameters of the COP
Admolecules
Eads/eV
adsorption mode total dispersion dO−Ti α, β
CAT top-on −2.90 −0.43 1.90 0°, 0°
SAL top-on −2.63 −0.30 2.07 0°, 53.5°
PTA top-on −2.99 −0.46 1.91 24.5°, 5.1°
TPA plane-on −3.92 −0.72 1.97 90°, 19.1°
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the two hydroxyl groups (Figure 2a). The catechol oxygen
atoms are then connected to two adjacent surface Ti5c ions with
the Ti5c−OCAT bond length of 1.90 Å, giving rise to a local C2v
symmetry of the adsorption complex. The released protons are
attached to the adjacent bridging O2c(a) atoms with the H−
O2c(a) bond length equal to 0.97 Å, without any significant
interaction with the catechol admolecule. The main axis of the
molecule is parallel to the surface normal [110] direction (α =
0°, Figure 2a), whereas the short axis is oriented along the
[001] direction (β = 0°, Figure 2a1).
Salicylic Acid Adsorption. The highest adsorption energy
(Eads = −2.63 eV with the dispersion part of −0.30 eV) for the
SAL admolecule is related with the bidentate bridging
attachment via the −COO− anchor with the hydroxyl group
remaining intact (Figure 2b). The both carboxyl oxygen atoms
are ligated to two adjacent surface Ti5c ions with the Ti5c−OSAL
bond length of 2.07 Å. The released proton is stabilized on the
nearby bridging O2c(a) atom (dH−O2c = 0.95 Å), with only a
negligible interaction with the SAL admolecule. Such bidentate
bridging geometry of a local Cs symmetry has already been
reported for r-TiO2(110) surface,60−62 and is typical for
adsorbed monocarboxylic acids, such as formic, acetic, or
benzoic ones. The orientation of the SAL molecule with respect
to the substrate, defined by the α = 0° and β = 53.5° angles
(Figure 2b1), corresponds to a rotated vertical conformation,
which results from the trade-off between the considerable
attraction, involving the −OH group and the bridging oxygen,
and the steric repulsion of the aromatic ring with the closed
shell surface O2c2− ions.
Phthalic Acid Adsorption. In the case of the PTA
admolecule a tilted binding mode (α = 24.5°) involving both
carboxyl functionalities was found to give rise to the most stable
Cs-geometry with dTi−O equal to 1.91 Å (Figures 2c,c1). The
two protons released upon the attachment produce surface
hydroxyls with the bond lengths equal to dH−O = 0.95 Å. They
are involved in quite strong hydrogen bonds with the adjacent
carboxylic oxygen atoms (dO···HO = 1.45 Å). The adsorption
energy for this conformation is equal to Eads = −2.99 eV with
the dispersion part of −0.46 eV.
Terephthalic Acid Adsorption. Contrary to the previous
admolecules, in the case of TPA the highest adsorption energy
(Eads = −3.92 eV) was found to be associated with the plane-on
geometry (α = 90°) shown in Figure 2d. The binding occurs
now through the carbonyl oxygen atoms of both carboxylic
groups and the surface Ti5c ions, resulting in a local C2
symmetry (Figure 2d1). The dispersion energy of −0.72 eV is
roughly twice bigger than for the vertically adsorbed species
(Table 1), which may be associated with the larger interaction
area between the substrate and the flat-lying admolecule. The
binding entails rotation of the carboxylic group by ∼80° along
the Ph−COOH axis, as it can be inferred from Figure 2d, and
the resultant Ti5c−OTPA bond length is equal to 1.97 Å. The
discharged protons are accommodated on the nearest bridging
oxygen atoms (O2c(a)), giving rise to two surface hydroxyls with
dH−O2c(a) = 0.99 Å and the OTPA···HO2c(a) hydrogen bond
length of 2.15 Å. The long axis of the TPA molecule is rotated
by the angle of 19.1° with respect to the [001] direction,
delineated by the rows of the bridging oxygen anions (Figure
2d1). Such adsorption mode allows the carboxylic groups of the
TPA admolecule to better interact with the surface Ti5c ions.
For all adsorbed organic molecules, no significant mod-
ification of the aromatic ring was observed. The only relevant
changes include the already mentioned rotation of the
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Figure 2. Most stable adsorption geometries of COP molecules on the r-TiO2(110) surface. Perspective views (a-d) of the topmost trilayers of
titanium dioxide and adsorbed molecules, together with top views (a1-d1). The surface atoms are colored as follows: oxygen−red, titanium−light
gray, hydrogen−yellow, carbon−black, bridging oxygen ions of the substrate−violet, ligand oxygen ions attached to the surface−green.
Table 2. Bond Orders, Bader Charges, and Surface Dipole Values for COP Molecules Adsorbed on the (110) Facet of r-TiO2
CAT
total bond order 0.57
qB/|e| 0.50
surface dipole moment μ/Debye (μx, μy, μz), 18.6 (0.53, 0.12, 18.6)
carboxylic groups and a slight reduction of the C−O bond
length (by ∼2%), resulting from deprotonation. Relaxation of
the rutile surface upon the adsorption was found to also be
rather small. Titanium ions involved in the binding moved
slightly toward the admolecule by about ∼0.01 Å, whereas the
positions of all other atoms remained essentially intact. For
each investigated COP@TiO2 assembly the total bond order
(between the organic molecules and the rutile (110) surface),63
the Bader charges (qB) on the admolecules produced upon the
attachment, and the resultant surface dipole values were
calculated.
The results collected in Table 2 show that the bidentate
attachment via two hydroxyl functionalities (CAT) or via the
bidentate ligation through the carboxyl group (SAL) leads to a
comparable bond orders (0.57 vs 0.54), whereas in the case of
COP molecules containing two carboxyls the bond order
obviously strongly depends on their mutual position in the
phenyl ring. For the ortho-position (PTA) and the top-on
attachment the bond order is much smaller (0.41) than for the
para-arrangement (TPA) and the plane-on ligation (0.63). The
Bader charge acquired by the adsorbed organic molecules
decreases in the sequence CAT > SAL > PTA > TPA, and is
well correlated with the EHOMO(COP) − EF(TiO2) energetic
distance (SI, Figure S6). It shows that an extensive charge
rearrangement accompanies the COP-titania surface inter-
action. The extent of the charge transfer is essentially controlled
by the nature of the binding group, and is favored by the
hydroxyl functionalities. The resultant surface dipole is the
highest for PTA, since the angular top-on configuration moves
the carboxylic oxygen atoms not involved in the binding back
Article
SAL PTA TPA
0.54 0.41 0.63
0.37 0.31 0.20
13.8 (−0.97, −1.35, 13.6) 22.3 (0.87, −8.64, 20.6) 8.18 (−0.28, 0.07, 8.18)
from the surface. The charge transfer and the surface dipole
generate local fields that give rise to the shift in the band edge
positions of the titania substrate (vide inf ra). The dipole
component of the COP admolecules normal to the surface
gives rise to a shift in the titania CB.
Electronic Structure of the Functionalized Rutile (110)
Surface. For an in-depth electronic level insight into the
influence of the COP molecules on self-sensitization of the
rutile nanorods, we discussed the energy level alignment and
the molecular coupling at the COP@r-TiO2 interface by
calculating the density of states (DOS) for distal and proximal
contact configurations (Figures 3−6). These results were used
to discuss possible implications of the different magnitude of
the electronic coupling between the pollutant molecules and
the TiO2 substrate in controlling the efficiency of forward and
back electron-transfer processes. Additionally, the charge
density contours of the CB and VB edges and those related
to the relevant orbitals of the COP species (HOMO, LUMO)
were also shown. For a better clarity, the corresponding DOS
diagrams for the bulk and bare surface of rutile (Figure S7) are
briefly discussed in the SI. The calculated bulk band gap of 2.4
eV at Γ-point for r-TiO2, being very close to previous
theoretical predictions (2.4 eV at GGA+U level),64 is yet
lower than the experimental one (3.01 eV),65,66 which is typical
for DFT calculations. Indeed, it is well-known that insufficient
cancellation of self-interaction correction leads to under-
estimation of the energy gaps, as discussed elsewhere in more
detail.64 The (110) surface band gap of 1.1 eV is much smaller
than the bulk value, which stems from a number of in-gap states
due to the broken Ti−O bonds. It is similar to the previously
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reported value of 1.57 eV obtained with cluster model of the molecular orbitals with a contribution to DOS from the organic
(110) rutile termination.67 The band edge energy levels of the admolecule larger than 3%. These are states located around −3
rutile support and the HOMO−LUMO energy levels of the eV (b1), −1 eV (b3), and 1 eV (b4). Both frontier orbitals of the
COP admolecules for all investigated samples are collected in CAT molecule were shifted upward in an uneven way (HOMO
Table 3. by 0.3 eV and LUMO by 0.6 eV). Because in the bound state
these orbitals formally are no longer frontier orbitals of the
Table 3. Band Edge Energy Levels (VBM and CBM) for COP molecule, in order to emphasize their derivation they are
Bare and COP Covered (110) Surface of r-TiO2, and the labeled “HOMO” and “LUMO” hereafter. Moreover, in the
Frontier Energy Levels of COP Admolecules (COPHOMO and middle of the conduction band, a new state with an appreciable
COPLUMO)a contribution of the catechol ligand appeared. The electron
density contours corresponding to the “HOMO” (b1) and
bare CAT@ SAL@ PTA@ TPA@ “LUMO” (b4) orbitals of the bare CAT are still strongly
eV TiO2 TiO2 TiO2 TiO2 TiO2
localized on the ligand and are very similar to their parent shape
VBM −3.17 −4.17 −4.38 −4.36 −4.76 at distal arrangement (Figure 3a). The electron density
CBM −2.01 −3.31 −3.46 −3.48 −3.63 contours at the very bottom of the conduction band consists
EFermi −2.85 −3.36 −3.82 −4.26 −4.38 essentially of titanium 3d states of the t2g manifold (b2),
COPHOMO − −3.43 −3.99 −4.46 −4.45 whereas the top of the valence band is dominated by the
COPLUMO − 0.92 −0.42 0.41 0.18 catechol “HOMO−1”. A strong π-type bonding between the
a
All values correspond to the Γ point. CAT admolecule and the substrate is clearly visible by
accumulation of the charge density between the catechol
CAT@r-TiO2. In Figure 3a and 3b, the partial density of states oxygen and the surface titanium atoms with the resultant bond
(pDOS) diagrams are presented, showing alignment of the order equal to 0.57.
adsorbed catechol energy levels with respect to the band The calculated sizable charge transfer between the
structure of the TiO2 (110) surface for distal and proximal admolecule and the substrate is equal to 0.50 |e|. It is
arrangements, respectively. In both diagrams, the green and the responsible for the appearance of a marked absorption band the
red lines denote the density of states for the rutile oxygen and in the UV−vis spectra at 450 nm (vide inf ra). On the other
titanium ions, respectively, whereas the navy blue contours hand, the “LUMO” states are significantly coupled to the
indicate the pDOS contribution of the catechol admolecule. continuum of the conduction band d-states, which shall favor
The gradient gray bars epitomize the width of the conduction electron injection form the photoexcited COP admolecule to
and valence bands of the TiO2 substrate. The positioning of the deep of the rutile substrate. However, a low density of titania
HOMO/LUMO energy levels of the catechol molecule with acceptor states in this region is rather inauspicious for the
respect to the edges of the rutile surface conduction and the efficient interfacial electron transfer (vide inf ra).
valence bands before attachment (Figure 3a), reveals a SAL@r-TiO2. In the case of the r-TiO2(110) surface
staggered (type II) band alignment. The HOMO level (a1) is functionalized with salicylic acid, the type II energy-level
situated in the band gap just below CB (0.1 eV), the HOMO− alignment (Figure 4a and 4b) is quite similar to that of the
1 at the top of VB, whereas the LUMO (a2) is placed ∼0.4 eV catechol system. In a distal configuration, the strongly localized
above the conduction band. Upon attachment, the type II highest occupied band (a1 in Figure 4a), distanced from the CB
alignment is essentially preserved. Considering the energetic minimum by 0.25 eV, has mainly the HOMO character of the
window of interest defined by the band gap and the conduction parent salicylic acid (cf. Figure S6b, SI). The band
band regions, following the literature, we report only the corresponding to the HOMO−1 orbital of the admolecule is

Figure 3. Partial DOS of the r-TiO2(110) surface slab model calculated for the catechol molecule at distal (a) and proximal (b) arrangements
showing the corresponding energy alignments. (a1) and (a2) are the charge density contours of the HOMO and LUMO orbitals of the catechol
molecule in the distal configuration, whereas (b1−b4) refer to the charge density contours corresponding to the most important states of the
proximal arrangement: (b1) “HOMO” of the admolecule, (b2) bottom of the titania CB, (b3) a CB state with an appreciable (>3%) contribution of
catechol, (b4) “LUMO” of the admolecule. On the DOS plots, the green and red lines refer to titanium and oxygen of TiO2 states, respectively,
whereas the blue color denotes the molecule contribution. Partial charge density contours are color coded to reveal if they are occupied (blue) or
empty (yellow).

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Figure 4. Partial DOS of the r-TiO2(110) surface slab model calculated for the salicylic acid molecule at distal (a) and proximal (b) arrangements
showing the corresponding energy alignments. (a1) and (a2) are the charge density contours of the HOMO and LUMO orbitals of the salicylic acid
molecule in the distal configuration, whereas (b1−b4) refer to the charge density contours corresponding to the most important states of the
proximal arrangement: (b1) “HOMO” of the admolecule, (b2) bottom of the titania CB, (b3) “LUMO” of the admolecule. On the DOS plots, the
green and red lines refer to titanium and oxygen of TiO2 states, respectively, whereas the blue color denotes the molecule contribution. Partial charge
density contours are color coded to reveal if they are occupied (blue) or empty (yellow).

Figure 5. Partial DOS of the r-TiO2(110) surface slab model calculated for the phthalic acid molecule at distal (a) and proximal (b) arrangements
showing the corresponding energy alignments. (a1) and (a2) are the charge density contours of the HOMO and LUMO orbitals of the phthalic acid
molecule in the distal configuration, whereas (b1−b4) refer to the charge density contours corresponding to the most important states of the
proximal arrangement: (b1) “HOMO” of the admolecule, (b2) bottom of the titania CB, (b3) a CB state with an appreciable (>3%) contribution of
phthalic acid, (b4) “LUMO” of the admolecule. On the DOS plots, the green and red lines refer to titanium and oxygen of TiO2 states, respectively,
whereas the blue color denotes the molecule contribution. Partial charge density contours are color coded to reveal if they are occupied (blue) or
empty (yellow).

positioned 0.2 eV above the VB edge, whereas the LUMO state
(a2) is situated on the top of the conduction band. Binding of
the SAL molecule moves the “HOMO” level (b1) by 0.2 eV
below the CB minimum (Figure 4b) and shifts the LUMO
orbital (b3) down by 0.15 eV. As expected, the bottom of the
CB is composed mainly of Ti d states (b2), whereas due to
stabilization of the HOMO−1 state upon ligation, the VB
maximum is dominated by the oxygen 2p states of rutile. The
mixing of “LUMO” and “HOMO” with the substrate states is
rather small, implying a weak coupling. Although it hinders
undesirable charge recombination with a hole center localized
on “HOMO”, such situation is less favorable for photoelectron
injection via “LUMO” channel, suggesting a nonadiabatic
mechanism of the interfacial electron transfer. Following de
Angelis,68 it can be therefore conceived that the photoelectron
injection should correspond to surface CB states localized close
to “LUMO”, for which a faster undesirable recombination with
5449
the oxidized dye can be expected, in comparison to deeply
localized bulk states.69 On the other hand, localization of the
“HOMO” orbital in the band gap, just below the CB edge,
facilitates significant charge transfer between the SAL
admolecule and the rutile substrate, revealed by the appearance
of a sizable light absorption in the visible region (Figure 8, vide
inf ra). The calculated partial charge on the SAL adspecies equal
to 0.37 |e| and the total bond order of 0.54 are in line with such
significant charge transfer.
PTA@r-TiO2. The electronic structure of the phthalic acid
adsorbed on the r-TiO2(110) in a distal setting with HOMO
(a1) and LUMO (a2) embracing the titania conduction band
(Figure 5a) resembles those previously found for the CAT or
SAL molecules. Yet, in contrast to CAT and SAL, upon the
ligation the HOMO state (b1) is significantly stabilized (by 0.9
eV) and placed on the top of VB (0.05 eV below the edge),
whereas there are no PTA related states at the bottom of CB
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Figure 6. Partial DOS of the r-TiO2(110) surface slab model calculated for the terephthalic acid molecule at distal (a) and proximal (b)
arrangements showing the corresponding energy alignments. (a1) and (a2) are the charge density contours of the HOMO and LUMO orbitals of the
phthalic acid molecule in the distal configuration, whereas (b1−b4) refer to the charge density contours corresponding to the most important states
of the proximal arrangement: (b1) “HOMO” of the admolecule, (b2) bottom of the titania CB, (b3) a CB state with an appreciable (>3%)
contribution of terephthalic acid, (b4) “LUMO” of the admolecule. On the DOS plots, the green and red lines refer to titanium and oxygen of TiO2
states, respectively, whereas the blue color denotes the molecule contribution. Partial charge density contours are color coded to reveal if they are
occupied (blue) or empty (yellow).

(b2). An extended pDOS features that can be traced back to
“LUMO” (b4) appeared in the upper part of the conduction
band, together with localized state with a sizable PTA
contribution (b3) placed lower by 0.45 eV with respect to b4.
As a result, there are no new localized states in the band gap.
The charge transfer and the total bond order of the PTA-TiO2
assembly are equal to 0.31 |e| and 0.41, respectively.
TPA@r-TiO2. The DOS structure of the r-TiO2 covered by
the plane-on adsorbed TPA molecules in distal placement is
presented in Figure 6a. The HOMO state is located on the top
of VB (a1), and the LUMO above the middle of the conduction
band (a2). There are also the same localized states with TPA
contribution at the upper part of CB. The binding of TPA does
not influence the position of “HOMO” appreciably (Figure 6b),
and its shape reveals rather weak coupling with the titania VB
orbitals (b1). Together with the titanium t2g states (b2), they
constitute the VB and CB edges. The TPA related “LUMO”
state, b4, is shifted to the upper part of the conduction band.
There are also empty states with significant contribution of
TPA, located in the upper part of the CB (exemplified by b3).
The electron density repartition shows that they are quite well
coupled with the corresponding acceptor levels of the
conduction band. The side-on attachment results in a
considerably smaller charge transfer (0.20 |e|) as a result of
the multiplicity of the TPA-TiO2 bonds in the largest bond
order (0.63), in comparison to other examined COP molecules
(Table 3).
In summary, the results of electronic structure analysis
showed that the “HOMO” levels are shifted to lower energies
with the increasing −COOH to −OH ratio, changing thereby
their positions dramatically from the level close to the CB
minimum to the top of VB. The surface band gap narrows in
the opposite direction, from 1.13 eV for TPA@r-TiO2 (nearly
the same as in bare TiO2) to 0.78 eV for CAT@r-TiO2. This
accounts quite well for the observed enhancement of the light
absorption of the visible region (vide inf ra). The difference
between the energies of the “HOMO” and the CB levels is
lower for CAT@r-TiO2 than for SAL@r-TiO2, and it implies a
bathochromic shift of the absorption onset observed with the
decreasing −COOH to −OH ratio. The nature of the
5450
anchoring groups of the COP admolecules has more influences
on the relative position of the “HOMO” than on the “LUMO”
states, with respect to the CB and VB edges. The “HOMO”
position can be systematically shifted from the CB to VB edge
through replacement of the −OH anchors by the −COOH
ones.
Charge Transfer. The calculated DOS structures for the
COP@r-TiO2 photocatalysts can be used to assess the
efficiency of possible electron transfer along the A and B
pathways. In order to favor a fast injection of the photoelectron
along the two-step pathway A, the COP donor level should be
well-immersed in the semiconductor manifold of the
unoccupied CB acceptor states, preferably in the region of
the high density of states.70,71 Following the literature, two
properties related to the molecular structure of the COP
admolecules, namely, the electron injection energy, ELUMO, and
the percentage of “LUMO” localized on the anchoring moiety,
are crucial.67,68 For all investigated molecules the high
“LUMO”-CB gap is adequate for a pronounced thermodynamic
driving force for the fast electron transfer. The dependence of
the injection efficiency on the “LUMO” energy with respect to
CB can be accounted for within the Newns−Anderson
model.52,53 The center of the projected rDOS distribution
corresponds to the energy of the effective “LUMO” of the COP
adspecies, which epitomizes the excited electron injection state,
was evaluated as the position of the fitted Lorentzian peak
(Figure 7). Within this model, the “LUMO” broadening, Γ,
gives an estimation of the electron transfer: τ = 1/Γ. The
calculated values, equal to 2.0, 2.7, 2.9, and 3.6 fs and the peak
positions with respect to EF are 4.67, 4.86, 4.48, and 4.35 eV,
for CAT, PTA, TPA, and SAL adspecies, respectively, show that
all COP molecules exhibit rather similar rates of the electron
transfer. The only remarkable difference is a more favorable
immersion of the PTA “LUMO” in the conduction band of the
rutile nanorods in comparison to the other COP admolecules.
It may be thus expected that for all investigated COP
molecules in their adsorbed state the “LUMO” energetic
position with respect to the CB manifold is favorable for a fast
photoelectron injection. There is also no substantial influence
of the anchoring groups (−OH, −COOH) on the electron
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Figure 7. Lorentzian fitting of the pDOS corresponding to the
approximated “LUMO” states of the COP admolecules, showing their
position with respect to schematically outlined DOS profile of the
COP@TiO2 assembly.
transfer rate. Furthermore, for all the COP species the VB is
dominated by the “HOMO” orbital of the admolecule, which is
beneficial for charge separation. As a result, we can expect some
UV sensitization effect along the two-step pathway A, but its
overall efficiency should be reduced by low intensity of the
solar light in the energy window above 3 eV, where this process
is expected to take place. However, formation of the new donor
states in the band gap associated with the “HOMO” level in the
case of the CAT and SAL admolecules (Figure 3 and 4) opens
the route for a parallel visible light sensitization via a direct
injection of the photoelectron according to ligand (“HOMO”
of COP) to metal (CB of TiO2) electron transfer (one step
pathway B). The corresponding absorption bands were indeed
observed in UV−vis spectra (vide inf ra). Inspection of Figure
3b shows that for CAT species, a unique localization of
“HOMO” just below the CB and HOMO−1 above the VB
levels are especially beneficial for this photosensitization
channel.
UV−vis Absorption. In order to study the light absorption of
the functionalized r-TiO2 nanorods, the UV−vis spectra were
measured (Figure 8). The bare nanorods show a significant
absorption of UV light (λ < 400 nm), due to a direct VB to CB
excitation of TiO2. The CAT@r-TiO2 sample shows the highest
absorption of the visible light, extending from 400 nm to ca.
600 nm, and the dark orange color of this sample is the most
intense (see inset in Figure 8). Absorption of visible light by the
SAL@r-TiO2 sample (light yellow) is less pronounced as the
tail of the absorption extends to ca. 550 nm. All other samples
remained practically white upon the functionalization. These
results are in agreement with the calculated DOS structure and
with those reported previously.72,73 A brief inspection of the
Figure 8 reveals that the −COOH/−OH ratio plays a crucial
5451
Article
Figure 8. Diffuse reflectance spectra of bare and modified rutile
nanorods together with the picture of the samples suspended in water
(inset).
role in the photosensitization of the rutile nanorods in the
visible region. The highest effect was observed in the presence
of two −OH groups (CAT), a medium one for the mixed
−COOH/−OH case (SAL), whereas for dicarboxylic mole-
cules (PTA and TPA), no effect was observed essentially.
Spectroelectrochemical Measurements. Determination of
the redox properties of the COP@r-TiO2 photocatalysts was
performed according to the method developed recently.74 The
platinum electrode covered with the tested material was
subjected to a slow potential sweep (0.5 mV·s−1). The
simultaneously measured changes of the reflectance signal at
780 nm, transformed into the Kubelka−Munk (K−M)
function, enabled determination of the potential at which
TiO2 was reduced (Figure 9). In this way, it is possible to probe
Figure 9. Normalized spectral changes at 780 nm (represented by
changes of the Kubelka−Munk function) recorded upon the potential
sweep from −0.6 to −1.5 V vs Ag/AgCl electrode.
the density of states of the photocatalyst, and the higher it is,
the steeper slope of the K−M curve is observed. An increase of
the light absorption below −1.0 V results from the reduction of
the energy states localized at the bottom of the conduction
band. They can essentially be identified with the position of the
b2 states in Figures 3−6, which are crucial for the driving the
dioxygen reduction. For SAL@r-TiO2 and PTA@r-TiO2, the
edge of the conduction band is shifted toward lower energies,
implying the lower efficiency of O2•− formation.75 CAT@r-
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Figure 10. Photocurrent as a function of the photoelectrode potential (vs Ag/AgCl) and incident light wavelength recorded for photoelectrodes
covered with (a) bare r-TiO2, (b) CAT@r-TiO2, (c) SAL@r-TiO2, (d) PTA@r-TiO2, and (e) TPA@r-TiO2. The red and blue areas correspond to
the anodic and cathodic photocurrents, respectively, whereas the white areas represent a zero net photocurrent.

TiO2 and TPA@r-TiO2 samples exhibit the band edge position in the case of TPA@r-TiO2 is quite small (compare Figures 2
close to that of r-TiO2, making the photoelectron transfer and 9).
faster. Yet, these changes are not very significant in the case of Photocatalytic Tests. Photocatalytic degradation of colorless
rutile. The appearance of the shoulder for CAT@r-TiO2 at organic pollutants was tested by monitoring the total organic
−1.2 V corresponds to an empty acceptor state separated from carbon (TOC) content in the COP@TiO2 assembly irradiated
the conduction band by strong interaction with catechol ligand. with UV−vis light (full light of XBO lamp). The initial
Photocurrent Measurements. The UV−vis-induced activity decomposition rate constants were 0.024, 0.013, 0.005, and
of the samples was examined by photoelectrochemical 0.004 min−1 for CAT, SAL, PTA, and TPA, respectively, as
measurements. The results shown in Figures 10a−e reveal derived from the degradation curves shown in Figure 11. Two
significant differences among the investigated samples in the classes of the pollutant molecules can be distinguished here,
generated photocurrent as the function of the applied potential depending on the photodegradation rate constant. Molecules
and the wavelength of the incident light. A pronounced containing hydroxyl anchoring group (CAT, SAL) degrade
photocurrent induced by the ultraviolet light is observed for all much faster than those with the carboxyl attachment only
materials. In the case of r-TiO2 modified with organic
molecules a cathodic to anodic photocurrent switching appears
at various potential range. Photocurrents generated by the
incident visible light are higher for the electrodes covered with
modified r-TiO2 compared to that of bare r-TiO2. The most
pronounced sensitization effect was observed for CAT@r-TiO2
(Figure 10b); however, the visible-light-induced photoactivity
of SAL@r-TiO2 (Figure 10c) is also significant when compared
to its photoactivity induced by light of 400 nm.
This observation remains in a good agreement with the
results of the DFT calculations. Because the “HOMO” orbitals
of the catechol and salicylic acids are situated within the
bandgap of r-TiO2, these modifiers act as the photosensitizers
of r-TiO2. The photocurrent map recorded for TPA@r-TiO2
material (Figure 10e) resembles that of r-TiO2. Although the
“HOMO” of TPA is also localized within the bandgap, the
experimental coverage of this modifier at the (110) facet is
significantly lower than the adsorption of other molecules (vide
supra), and therefore, the influence of terephthalic acid on
photoelectrochemical properties of r-TiO2 is less significant.
Lower values of measured photocurrents are very likely the
consequence of a higher hydrophobicity of TPA@r-TiO2
material, which stems from the unique plane-on adsorption.
In this mode, both polar groups are anchored with the surface,
whereas the aromatic moiety is exposed to the solution. Also
the charge density flow between the organic molecule and the Figure 11. Self-decomposition of COP substrates: relative changes of
r-TiO2 crystal (ΔqB = 0.20 |e|) is less efficient than in the case total organic carbon content as the function of irradiation time
of other molecules, and therefore, the photosensitization effect (irradiation: full light of xenon lamp).

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(PTA, TPA). These results show also that the photo-
sensitization of the rutile nanorod catalyst via the direct
pathway B is much more efficient than the two step process
that involves the pathway A. It should be noted that the
influence of the sensitization on the photocatalytic decom-
position rate is most pronounced at the beginning (early stage)
of the degradation process when all pollutant molecules are not
fragmented significantly yet and thus can act as the self-
photosensitizers.
In order to elucidate the fate of the COP adspecies upon
irradiation, we investigated photoinduced chemical changes in
the SAL@r-TiO2 sample (taken as an example) by in situ DRS
measurements. The resultant differential spectra are presented
in Figure 12. As a reference, we added the differential spectra of
Figure 12. Differential UV−vis spectra of SAL@r-TiO2 in the solid
state recorded for different photoreaction times (up to 60 min) (a)
together with reference differential spectra of r-TiO2 functionalized
with various organic molecules containing two hydroxyl groups: 2,3-
dihydroxybenzoic acid (2,3-DHB), 2,5-dihydroxybenzoic acid (2,5-
DHB), and catechol (CAT) with the subtracted SAL@r-TiO2 (for the
sake of a direct comparison) (b).
r-TiO2 functionalized with various organic molecules contain-
ing two hydroxyl groups, such as 2,3-dihydroxybenzoic acid
(2,3-DHB), 2,5-dihydroxybenzoic acid (2,5-DHB), and cat-
echol (CAT) with the subtracted SAL@r-TiO2 (for the sake of
a direct comparison). Gradual development of a broad
pronounced band in the range of 400−800 nm, characteristic
for dihydroxybenzene derivatives, reveals a progressive
insertion of the photogenerated hydroxyl groups into the
aromatic ring of the SAL admolecules during the photocatalytic
reaction. As it was discussed above, this explains the observed
bathochromic shift of the absorption with the increasing −OH/
−COOH ratio. As a result, the “HOMO” position is shifted
toward the conduction band edge, which is beneficial for more
effective utilization of the visible range of the solar light, via
ligand (“HOMO” of COP) to metal (CB of TiO2) electron
transfer. This observation reveals also an autocatalytic stage of
COP self-degradation that results from specific tuning of the
band alignment between the photohydroxylated COP and the
rutile moieties of the photocatalyst. It promotes localization of
the hole on the organic component facilitating immediate
reaction with water, [COP−H]•+ + OH− → COP−OH + H•.
As a result, a doubly hydroxylated aromatic ring system is
5453
Article
formed, similar to that of catechol that was found to be
beneficial for the visible photosensitization of the system.
Upon the prolonged irradiation, the photodegradation rates
become comparable (Figure 11), because the sensitization
effect ceases due to gradual deterioration of the COP
admolecules into smaller fragments absorbing UV only and
finally to CO2 and H2O end-products. To the best of our
knowledge, the nature of such photocatalytic self-degradation in
the case of the colorless organic compounds has not been
elucidated until now using jointly experimental and theoretical
approaches.
■ CONCLUSIONS
By combining several photoelectrochemical and spectroelec-
trochemical techniques with the DFT molecular modeling we
probed the electronic nature of self-sensitization of rutile
nanorods by small colorless organic pollutants, providing a
comprehensive background for mechanistic understanding of
their photodegradation. We selected disubstituted benzene
derivatives with −OH and −COOH groups (i.e., catechol,
salicylic acid, phthalic acid, and terephthalic acid) as model
colorless pollutants. The role of the anchoring groups (−OH
and −COOH) was explained in terms of one-step (HOMO →
CB) and two-step (HOMO → LUMO → CB) photo-
sensitization mechanisms. It was shown that the attachment
by hydroxyl groups triggers the one-step pathway via a direct
ligand to metal charge transfer (CAT, SAL). The presence of
carboxyl anchors, in turn, favors the two step sensitization
involving intramolecular excitation followed by the photo-
electron injection from LUMO to CB. The carboxyl anchors
locate the LUMO state at the top of the conduction band
making the two step pathway less efficient due to the low
overlap with the solar spectrum (far UV), despite the fast
electron transfer (2−4 fs). The efficiency of self-sensitized
degradation of disubstituted benzene derivatives decreases in
the order: (−OH, −OH) > (−OH, −COOH) > (−COOH, −
COOH), in an excellent agreement with the theoretical and
experimental predictions. As the result the molecular under-
standing of photocatalytic degradation of small pollutants
showing a crucial role of the anchoring and photogenerated
hydroxyl groups in the self-sensitization process was accounted
for with an unprecedented comprehensive way. It was shown
that at early stages of the photocatalytic degradation process the
aromatic rings of the COP moieties are readily photo-
hydroxylated, fostering the visible light utilization. Such
autocatalytic hydroxylation processes can also be relevant for
photocatalytic degradation of those pollutants that originally do
not exhibit hydroxyl functionalities.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b10983.
TEM image simulation conditions; relaxation of the bare
(110) surface of rutile TiO2; XRD, Raman, and FTIR
spectra for unmodified and modified r-TiO2 nanorods;
calculations of pollutants coverage; the details of the
electronic structure for the set of gas phase COP
molecules; starting geometries for COP deposition;
Bader charge (qB) vs the EHOMO(COP) − EF(TiO2)
plot; DOS diagrams for bulk and bare surface titania
(PDF)
DOI: 10.1021/acs.jpcc.5b10983
J. Phys. Chem. C 2016, 120, 5442−5456
The Journal of Physical Chemistry C
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: zasada@chemia.uj.edu.pl. Tel.: +48 12 663 20 73.
*E-mail: macyk@chemia.uj.edu.pl. Tel.: +48 12 663 22 22.
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The support from the Foundation for Polish Science within the
TEAM/2012-9/4 project, cofinanced by the EU European
Regional Development Fund, is highly acknowledged. A part of
the work (photocatalytic tests) was financed by the National
Science Centre, Poland, within the grant number 2011/01/B/
ST5/00920. M.B. acknowledges the financial support by FP7
EU project 4G-PHOTOCAT (309636). The authors want to
dedicate this paper to professor Elio Giamello from University
of Torino to honor his 65th anniversary.
■
ABBREVIATIONS
BG, band gap; CAT, catechol; CB, conduction band; COP,
colorless organic pollutants; DFT, density functionals theory;
DFT+D, density functionals theory with inclusion of dispersion
forces; DFT+U, density functionals theory with Hubbard
correction; EF, Fermi Energy; SI, Supporting Information;
GGA, General Gradient Approximation; ITO, indium tin oxide;
PAW, Plane Augmented Wave; PTA, phthalic acid; r-TiO2,
rutile phase of TiO2; SAL, salicylic acid; TEM, transmission
electron microscopy; TPA, terephthalic acid; VB, valence band;
XC, eXchange-Correlation
■
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J. Phys. Chem. C 2016, 120, 5442−5456