Zahed I 2015
Zahed I 2015
Zahed I 2015
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Hojamberdiev and M. Bekheet, RSC Adv., 2015, DOI: 10.1039/C5RA13763B.
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DOI: 10.1039/C5RA13763B
a
Department of Physical Chemistry, Shahrood Branch, Islamic Azad University, Shahrood, Iran
b
Department of Environmental Science and Technology, Faculty of Engineering, Shinshu
c
Fachgebiet Keramische Werkstoffe, Institut für Werkstoffwissenschaften und –technologien,
Berlin, Germany
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ABSTRACT
The structure, electronic and optical properties have been studied to consider photocatalytic
activity of three-layer perovskite Dion-Jacobson phase CsBa2M3O10 (M = Ta, Nb) using the
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density functional theory (DFT) method with the plane-wave pseudo-potential in the frame of the
GGA proposed by Perdew, Burke, and Ernzerhof (PBE). CsBa2Ta3O10 and CsBa2Nb3O10 are
ionic. According to the symmetry breaking of MO6 octahedra from Oh point group to
centrosymmetric (D4h) and non-centrosymmetric (C4v) point groups, the generation of local
internal fields, the promotion of electron-hole pairs separation in the very initial process of
photo-oxidation and the improvement in photocatalytic activity are suggested. Site and angular
projected density of states for CsBa2M3O10 show that the valence and conduction bands are made
mainly of O and M orbitals, therefore the presence of dipole moment at the MO6 octahedra will
play an important role in separating of electrons and holes. According to the optical properties
simulation the origin of interband transitions for CsBa2Ta3O10 and CsBa2Nb3O10 are from O-p and
plasmon energies 13.16 and 12.07 eV, respectively, which can possibly oxidize/decompose
KEYWORDS:
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1. Introduction
Perovskites are inorganic compounds with a general chemical formula ABX3, where A and B are
two cations of different sizes and X is an anion, usually oxygen, that bonds to both cations. Most
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perovskites have a cubic symmetry structure in which the B cation is in 6-fold coordination
distortion, such as tilting of BO6 octahedra, can reduces the coordination number of A and B cations
or both. The orthorhombic and tetragonal structures of perovskites are the result of changes in the
coordination numbers of cations. Perovskites can also have layered structures constructed of
negatively charged thin layers and cations in the interlayer space compensating negative charges
on the layers According to their chemical nature, three types of layered perovskites are known with
A′[A n −1Bn O3n +1 ] Dion-Jacobson (DJ) phase, and A′2 [A n −1B n O3n +1 ] Ruddlesden-Popper (RP)
phase; where Aʹ is monovalent alkali metal ion, A is divalent alkaline earth metal ion, and B is
tetravalent or pentavalent transition metal ion. In the AV phase, the intruding layer is
[Bi 2O 2 ]2 + ion, whereas the intruding layer is an alkali metal in the DJ and RP phases. In the DJ and
RP phases, the thickness of perovskite slabs relies on the number of BO6 octahedral (n) corner
1-4
shared along the c-axis . The DJ and RP layered perovskites have various interesting physical
and chemical properties, such as ionic conductivity due to ion exchange of alkali ions with molten
3
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2. Computational methodology
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The experimental crystal structural data of CsBa2M3O10 (M = Ta, Nb) were taken as initial
geometries 1, 6. The Cambridge Serial Total Energy Package (CASTEP) code 7, which uses a plane
(GGA) of Perdew, Burke, and Ernzerhof (PBE) was used for the electronic exchange-and
correlation interactions 8. The core-valence interactions were described by the Vanderbilt ultrasoft
pseudo-potential 9 with the valence configurations 5s2 5p6 6s1 for Cs, 5s2 5p6 6s2 for Ba, 4s2 4p6 4d4
5s1 for Nb, 5s2 5p6 5d3 6s2 for Ta and 2s2 2p4 for O, in order to allow calculations to be performed
with the lowest possible cut-off energy with minimum contribution from the core region. The
crystal reciprocal-lattice and integration over the Brillouin zone were performed using the
Monkhorst-Pack 10 grid of 12 × 12 × 3 for CBTO and 13 × 13 × 3 for CBNO, in which the spacing
of grid points was smaller than 0.03 Å-1 for all calculations. The
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Broyden-Fletcher-Goldfarb-Shanno (BFGS) algorithm has been used for geometry
optimizations, and the convergence parameters were as follows: the plane wave basis set energy
cut-off 550 eV, total energy convergence tolerance 1 × 10-5 eV/atom, self-consistent field tolerance
2 × 10-6 eV/atom, maximum force 0.03 eV/Å, maximum stress 0.05 GPa, and maximum
displacement 0.001 Å. The separation between k-points in the band structure calculations was
The conventional cell of the DJ phase CsBa2M3O10 (M = Ta, Nb) is displayed in Figure 1a.
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(a)
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D4h C4v
Figure 1. (a) Crystal structure and corresponding polyhedron structure of Dion-Jacobson phase
CsBa2M3O10 (M = Ta, Nb). The cesium, barium, tantalum/niobium, and oxygen atoms are
represented by purple, green, blue, and red spheres, respectively. In the polyhedron structure, MO6
octahedral environments are shown by blue color. (b) Distortion of MO6 octahedral (Oh) to
centrosymmetric (D4h) and non-centrosymmetric (C4v). The tantalum/niobium and oxygen atoms
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The crystalline structures of tetragonal CBTO and CBNO with space group of P4/mmm (No. 123)
contain one cesium atom, two barium atoms, three tantalum/niobium atoms, and ten oxygen
atoms in a unit cell. In these crystal structures, Cs and Ba atoms are in environment of MO6
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octahedral units, in which there are one type of Cs atom (1 atom with site of 1d), one type of Ba
atom (2 atoms with site of 2h), two types of M atoms (1 atom with site of 1a and 2 atoms with
atoms with site of 4i). The optimized crystallographic parameters and final atomic positions of
tetragonal CBTO and CBNO are listed in Table 1 and compared with the experimental values.
Table 1. Optimized crystallographic parameters and final atomic positions of tetragonal CBTO
and CBNO compared with the experimental values from Ref. [1,6]*
Wyckoff
Crystallographic parameters Atom x y z
position
CsBa2Ta3O10 (CBTO) Cs 1d 0.5 (0.5) 0.5 (0.5) 0.5 (0.5)
a = 4.1362 (3.9647) Å Ba 2h 0.5 (0.5) 0.5 (0.5) 0.1439 (0.1442)
b = 4.1362 (3.9647) Å Ta (1) 1a 0.0 (0.0) 0.0 (0.0) 0.0 (0.0)
c = 16.2527 (15.7392) Å Ta (2) 2g 0.0 (0.0) 0.0 (0.0) 0.2847 (0.2985)
α=β=γ=90˚ O (1) 2f 0.0 (0.0) 0.5 (0.5) 0.0 (0.0)
O (2) 2g 0.0 (0.0) 0.0 (0.0) 0.1272 (0.1280)
O (3) 4i 0.0 (0.0) 0.5 (0.5) 0.2587 (0.2680)
O (4) 2g 0.0 (0.0) 0.0 (0.0) 0.4009 (0.4030)
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As shown, the calculated crystallographic values and atomic positions are close to the
experimental values. The main difference between the theoretical and experimental values is due
to two factors: i) the experimental measurements were performed at 298 K, while the theoretical
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calculations were done in the ground state condition under absolute zero temperature and ii) the
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known DFT limitation is due to certain simplifications and approximations . The crystal
parallel to the c-axis, which are linked by apex oxygen. The calculated and experimental results in
Table 2 showed that the MO6 octahedra in CBTO and CBNO is distorted from Oh point group to
centrosymmetric (D4h) and non-centrosymmetric (C4v) point groups, as shown in Figure 1b. The
interlayer cesium ion is located in the channel between four C4v polyhedra, whereas barium ions
are located in the channel between two D4h and two C4v polyhedra. In the MO6 group with D4h
point group the axial M–O bond lengths are slightly different than that of equatorial M–O bonds,
and the O–M–O bond angles are exactly 90°. The calculated M–O bond lengths in Table 2 show
that the axial and equatorial M–O bond lengths in CBTO are 2.068 and 2.067 Å, respectively,
whereas for CBNO are 1.975 and 1.996 Å. Therefore, the center of gravity is located at the M
position, and consequently, dipole moment in the local MO6 groups with D4h point group is zero.
On the other hand, in the MO6 group with C4v point group, two axial M–O bond lengths are
significantly different, that is, 2.559 and 1.889 Å for CBTO and 2.696 and 1.761 Å for CBNO.
Also, the equatorial M–O bond lengths are 2.111 and 2.034 Å for CBTO and CBNO, respectively.
The various M–O bonds and the deviated M–O–M angles from 90° lead to the centers of the
positive and negative charges not locating at the same point. The separation between the centers of
the positive and negative charges generates dipole moment in the local MO6 groups with C4v point
group. The local internal fields due to the dipole moments are suggested to promote the separation
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of electron-hole pairs in the very initial process of photo-oxidation and to improve photocatalytic
activity 13.
Table 2. The calculated Mulliken bond population, population ionicity, and bond lengths of
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tetragonal BCTO and BCNO compared with the experimental values from Ref. [1,6]
To understand the bonding nature of each M–O bond, the Mulliken bond populations were
calculated. The Mulliken bond population is a measure of spatial charge density between bonding
atoms, and this quantity does not totally depend on the valence charge transfer along the bond
axis 14. A high total overlap (bond) population indicates a high degree of covalency in the bond,
and the positive and negative values indicate bonding and antibonding states, respectively 15. On
the other hand, the percentage of covalence nature of a bond can be calculated using population
P −P
− c
P
Pi = 1 − e (1)
where P is the total overlap population of the bond and Pc is the bond population for a pure
covalent bond. The lower limit, i.e., Pi = 0 indicates a pure covalent bond, whereas the upper limit
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i.e., Pi = 1 indicates a pure ionic bond. Here, the value of Pc is assumed to be equal to 1. The
calculated total overlap population and population ionicity of each M–O bond in tetragonal
CBTO and CBNO are also given in Table 2. It is found that Ta2–O1 (ax), Nb1–O1 (ax), and Nb2–O1
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(ax) are pure ionic bonds, whereas Ta1–O1 (ax) and Ta2–O4 (ax) are pure covalent bonds.
Moreover, Ta1–O2 (eq) and Nb2–O4 (ax) bonds have ionic-covalence and highly covalent nature,
It is known that the Kohn-Sham band structure underestimates systemically the band gap of
16
insulators and semiconductors by about 30-100% due to the known shortcoming of
17
exchange-correction function in describing excited states . To illustrate the problem, the
underestimated band gap can be corrected by scissors operator according to the experimental
values. This operator rigidly shifts the unoccupied conduction band states with respect to the
completely occupied valence band states to bring the minimum band gap in line with
experimental values. Diffuse reflectance UV-vis spectroscopy is a simple method for measuring
the experimental band gap. The observed experimental UV-Vis absorption spectra for CBTO and
CBNO samples are shown in Figure 2a, and the experimental band gaps can be calculated using
1239.84
Eg = (2)
λ cut off
The measured UV-Vis absorption cut-off wavelengths for CBTO and CBNO samples are about
The calculated band structures of CBTO and CBNO along the high symmetry directions in the
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(a)
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Z A M G Z Z A M G Z
(c)
Figure 2. (a) Experimental UV-Vis absorption spectra of CBTO (blue) and CBNO (red). The
cut-off wavelength positions are shown by arrows. (b) The calculated band structures of CBTO and
CBNO. The Fermi energy (EF) is set to be 0 eV and is marked by a horizontal dashed line. (c) The
first Brillouin zone of CBTO and CBNO in the reciprocal lattice. The red line corresponds to the
path of the band structure diagram, and g1, g2, and g3 denote the reciprocal vectors.
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The Fermi energy level, EF, is chosen to be located at the position of 0 eV. The coordinates of the
special points of the Brillouin zone (Figure 2c) in terms of unit vectors of the reciprocal lattice
are G (0, 0, 0), Z (0, 0, 0.5), R (0, 0.5, 0.5), X (0, 0.5, 0), A (0.5, 0.5, 0.5), and M (0.5, 0.5, 0). For
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CBTO and CBNO, the uncorrected band gap energies are 1.42 and 1.49 eV, respectively, which
are smaller than the experimentally obtained band gap energies. Therefore, the underestimated
respectively. As shown in Figure 2b, for CBTO and CBNO, the valence band maximum (VBM)
and conduction band minimum (CBM) are located at different points of the Brillouin zone,
indicating that these compounds are indirect band gap semiconductors. The second derivative of
band dispersion band-edge energy as a function of the wave vector k is related to the inverse of
effective mass of electron or hole at the band extremes. For tetragonal crystals, the effective masses
18
of either the hole or electron in the [100], [010] directions are equal . As can be seen from the
graphical view of band structures, the valence and conduction bands in the [0 0 1] direction are
almost flat and less dispersive compared to the [0 1 0] and [1 0 0]. The higher dispersive
characteristics of the conduction and valence bands along the [0 1 0] and [1 0 0] directions
indicate the low effective masses of electrons and holes in the CBTO and CBNO with respect to
the [0 0 1] direction. On the other hand, the recombination of photo-generated charge carriers
along the [0 0 1] direction in the CBTO and CBNO semiconductors with indirect band gaps are
inefficient.
In order to analyze the composition of the electronic band structures, the corresponding total,
site- and l-projected density of states (DOS) diagrams and their projected electronic wave
functions (PEWF) are shown in Figures 3-6. It is exigent to mention that the plane wave basis set
and ultrasoft pseudo-potential present only the wave functions of the valence electron of atoms.
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The total DOS diagrams and their PEWFs in the (1 0 0) plane for CBTO and CBNO are presented
(a) E3
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E2 E5
E6
(b)
CBTO
CBNO
Figure 3. (a) Total density of states for CBTO (red) and CBNO (blue). The Fermi energy (EF) is
set to be 0 eV. (b) Total charge density distribution for CBTO and CBNO in the (1 0 0) plane in
It can be seen that the charge density contours for O and Ba atoms in the (1 0 0) plane containing
O, Ba, and Cs atoms are spherical, suggesting a highly ionic bonding nature for O–Ba. On the
other hand, the charge density contours in the (1 0 0) plane containing O and M atoms
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corroborate that there are highly ionic and highly covalent characters between O and M atoms in
different O–M interactions. The analysis of PEWF indicates that the bonding nature in CBTO and
The site- and l-projected DOS diagrams together with their PEWFs for conduction band
minimum and five parts of valence band are shown in Figures 4-6. For both systems, the quality
of PDOS results is similar. The lowest-lying state from -20 to -18 eV (E1 region) is mainly due to
Cs-5s and Cs-6s states. The second region in a higher energy range (E2 region) from -18 to -15 eV
is essentially contributed by O-2s states with a minor admixture of Ba-5p and Ta-5s/6s/5p/5d
states for CBTO or Nb-4s/5s/4p/4d states for CBNO. The PEWF of this region shows a weak
hybridization between O atom and Ba, Ta or Nb atoms forming an ionic bonding. The next region
(E3 region) from -11 to -9 eV mainly comes from Ba-5p states with a small contribution of O-2s
states. The PDOS and PEWF of this region show weak s-p hybridization between O and Ba atoms
forming an ionic bonding. The E4 region is predominantly composed of Cs-5p which is slightly
hybridized with O-2p. The role of Ta or Nb electronic states in this energy region is very minor.
At the top of valence band (E5 region), O-2p is overlapped with Ta-5d or Nb-4d, indicating p-d
hybridization between O and Ta or Nb atoms forming a covalent bonding. The conduction band
region (E6 region) is mainly from O-2p and Ta-5d or Nb-4d states. Since the valence and
conduction bands (E5 and E6 regions) are mainly composed of O and Ta or Nb orbitals, the band
gap excitation can occur at the MO6 units; consequently, the presence of a dipole at the MO6
(a) (b)
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blue lines represent s, p, and d orbitals, respectively. The Fermi energy (EF) is set to be 0 eV.
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E6
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E5
E3
E2
E1
Figure 5. Projected wave function contour plots for CBTO at six different energy ranges in the (1
E6
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E5
E3
E2
E1
Figure 6. Projected wave function contour plots for CBNO at six different energy ranges in the (1
The optical property of a system is related to the transverse dielectric function ε(q,ω), where q is
the momentum transfer in the photon-electron interaction and ω is the angular frequency for
excitation. When the momentum transfer from the initial state to the final state is neglected, the
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complex dielectric function can be defined by the following mathematical relation 20:
optical transitions between the different special k points at the first irreducible Brillouin zone.
The intraband transitions are only important for metals; therefore, only direct and indirect
interband transitions can be considered for semiconductors21, 22. ε2(ω) can be calculated from
direct numerical evaluations of the momentum matrix elements of the electric dipole operator
between the conduction and valence band wave functions 23, 24:
2e 2 π 2
ε 2 (ω ) = ∑
ωε 0 k , v,c
ψ ck u.r ψ kv δ(E ck − E kv − E) (4)
where u is the polarization vector of the incident electric field, r is the electron’s radius vector,
and e is electric charge, ψ ck and ψ kv are the conduction and valence band wave functions at k,
respectively, and ε0 is the vacuum permittivity. The summation of the equation is applied over all
states from the occupied and empty bands, with their wave functions obtained in a numerical
form after the optimization of the crystal structure. The real part, ε1(ω), of the dielectric function
can be obtained from the imaginary part by using the Kramers-Krönig dispersion equation 24, 25:
2 ∞ Ω ε 2 (Ω )
π ∫0 Ω 2 − ω 2
ε1 (ω) = 1 + P dΩ (5)
All optical properties were calculated with calculation geometry polycrystalline, instrumental
smearing 0.5 eV. The vertical rigid shift of conduction band states (scissors operators) 2.12 and
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1.25 eV was applied for CBTO and CBNO, respectively, due to underestimation of excitation
energies with the DFT calculations. Figure 7a shows the calculated average imaginary and real
parts of dielectric constant of CBTO and CBNO. The real part of dielectric function at zero
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frequency shows that the static dielectric constants for CBTO and CBNO are 2.856 and 2.904,
respectively. The square root of static dielectric constant gives an estimation of the refractive
part of dielectric function are due to damping of electromagnetic wave, and zero values indicate
that longitudinally polarized waves are possible 20. The imaginary part of dielectric function starts
at 3.86 and 3.18 eV for CBTO and CBNO, respectively. Since the direct interband transitions
have a significant contribution to the ε2(ω) with respect to indirect interband transitions, the
maximum of the main peak for CBTO and CBNO belongs to A → A and M → M direct
transitions. The main portion of the mentioned peaks for CBTO and CBNO is due to O-2p → Ta-5d
and O-2p → Nb-4d interband transitions, respectively, whereas Ta-5d → O-2p and Nb-4d → O-2p
interband transitions have smaller portion. In the electromagnetic radiation, electric and magnetic
fields oscillate perpendicular to each other and perpendicular to the wave propagation. Interband
and intraband transitions are resulted from the effect of electric field of photon on the complex
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(a)
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(c)
Figure 7. (a) Real (solid line) and imaginary (dashed line) parts of the dielectric function of
CBTO (red line) and CBNO (blue line). (b) Energy loss functions of CBTO (red line) and CBNO
(blue line) as a function of photon energy. (c) Absorption spectra of CBTO (red line) and CBNO
When electrons pass through a homogeneous material, some electrons undergo inelastic scattering
which means that they loss energies, also their paths slightly and randomly deflect. The energy loss
−1 ε 2 ( ω)
L(ω) = Im = (6)
ε (ω) ε1 (ω) + ε2 (ω)
2 2
located at 13.16 and 12.07 eV for CBTO and CBNO, respectively, where electrons are originally
unbound to their lattice sites and start plasma oscillation. The collective oscillations of free electron
gas density is plasmon, and the corresponding energy is so-called plasmon energy (Ep). The values
The quantity and nature of the optical band gap can be calculated using the conventional Tauc
method from the optical absorption spectra. The absorption coefficient α(E) indicates the fraction
of absorbed light when it passes through the material, and is written as 24:
where c is the velocity of light. Two types of optical transitions, direct and indirect, can be
where A and B are fitting parameters, Egdirect and Egindirect are direct and indirect optical gaps, Ephonon
is the phonon energy and E is incident photon energy. The straight line segment in (αE)2 indicates a
direct optical band gap, whereas the straight line segment in (αE)0.5 indicates an indirect optical
band gap.
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The calculated optical absorption curves in Figure 7c show that the CBTO and CBNO are poor
absorber of visible light, or in other words, are ultra violet (UV) light-responsive photocatalysts.
29
Based on ISO standard ISO-21348 , main absorption of incident photon for CBTO and CBNO
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occurs at the vacuum ultra violet region. Extrapolation of the linear portion of Tauc plots (Figure
8) with the abscissa clearly indicates that CBTO and CBNO are indirect semiconductors so that
CBNO can absorb near UV light and violet light in the visible region, respectively.
(a)
(b)
Figure 8. Tauc plots of (a) CBTO and (b) CBNO. (αE)0.5 for indirect gap (blue line) and (αE)2 for
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The positions of valence and conduction bands of a semiconductor and the redox potentials of an
adsorbate are important factors for the oxidation and reduction capabilities of the semiconductor
to undergo photoinduced electron transfer to the adsorbed species on its surface. The suitable
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potential level of the acceptor species is thermodynamically required to be more positive than the
conduction band potential of the semiconductor (ECB), while the potential level of the donor
where Ee is the energy of free electrons on the hydrogen scale (approximately 4.50 eV) and χ is
1
P P
χ ≈ Π χ k (11)
k =1
electronegativity of CBTO and CBNO are 5.40 and 5.37 eV, respectively, which were calculated
from the experimental values of electronegativity (i.e., Ba = 2.40 eV, Cs = 2.18 eV, Ta = 4.11
37
eV, Nb = 4.00, and O = 7.54 eV) . The relative dispositions of VB and CB edge potentials of
CBTO and CBNO with respect to vacuum scale and NHE (normal hydrogen electrode) are
displayed in Figure 9.
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O2 + 2e → O2•- E° = -0.33 V
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2H+ + 2e → H2 E° = 0.00 V
Figure 9. Relative dispositions of VB and CB potentials of CBTO and CBNO with respect to
From the viewpoint of positions of VB and CB edge potentials, CBTO and CBNO are suitable
photocatalysts without the need for co-catalysts. The VB potentials of CBTO and CBNO are more
positive than the oxidation potential of O2/H2O (1.23 V), H2O2/H2O (1.77 V), and O3/H2O (2.07
V). Therefore, the photogenerated holes can oxidize H2O to produce active species O2, H2O2, and
O3. These active species can further oxidize/decompose organic pollutants and dye molecules. The
CB potential of CBTO is more negative than the redox potential of H2O/OH• (-0.83 V); therefore,
the photogenerated electrons can produce H2 and active species O2•- and OH•, while the
photogenerated electrons in CBNO can produce H2 and O2•-. In addition to O2•- and OH• are active
species to decompose organic pollutants, CBTO and CBNO are good candidate for photocatalytic
4. Conclusions
phase CsBa2M3O10 (M = Ta, Nb) have been studied with the plane wave pseudo-potential using the
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density functional theory (DFT) method considering the exchange-correlation function within the
generalized gradient approximation (GGA) proposed by Perdew, Burke, and Ernzerhof (PBE), as
(D4h) and non-centrosymmetric (C4v) point groups, leading to the special optical properties and
photocatalytic activities. The population ionicity index indicated that there are different
percentages of covalence nature in the M–O bonds from pure covalent to pure ionic. The band
structures and Tauc plots showed that CsBa2Ta3O10 and CsBa2Nb3O10 are ultra violet (UV)
light-responsive photocatalysts with indirect band gap. The density of states spectrums and
projected electronic wave functions were studied in detail to illustrate the origin of photocatalytic
activity and nature of M–O and Ba–O bonds. CsBa2Ta3O10 and CsBa2Nb3O10 with plasmon
energies of 13.16 and 12.07 eV, respectively, were suggested to possibly oxidize/decompose
organic pollutants and generate hydrogen from water splitting under UV light.
14. J. He, E. Wu, H. Wang, R. Liu and Y. Tian, Phys. Rev. Lett., 2005, 94, 015504.
15. S. Goumri-Said, H. Ozisik, E. Deligoz and M. Benali-Kanoun, Semicond. Sci. Technol.,
2013, 28, 085005.
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RSC Advances Page 26 of 26
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DOI: 10.1039/C5RA13763B
This work discloses structural, electronic and optical properties of three-layer perovskite Dion-
Jacobson phase CsBa2M3O10 (M = Ta, Nb) using the DFT method. These semiconductors are
UV-light-responsive photocatalysts.