Springer Nature 2021 LATEX template

Zn-doping and oxygen vacancy effects on the

reactivity and properties of monoclinic and
tetragonal ZrO2: a DFT study
Rafael R. C. Mancera1 , Viviane S. Vaiss1*, Oliver E. E.
Espino2,3 , Roberto. R de Avillez2 , Lucia G. Appel3
and Luciano T. Costa1*
1 Instituto de Quı́mica, Universidade Federal Fluminense, Campos
de Valonginho s/n, Centro, Niterói, 24020-14, Rio de Janeiro,
Brazil.
2 Departamento de Engenharia Quı́mica e de Materiais, Pontifı́cia

Universidade Católica do Rio de Janeiro, Rua Marquês de São

Vicente, 225, Gávea, Rio de Janeiro, 22451-900, Rio de Janeiro,
Brazil.
3 Divisão de Catálise, Biocatálise e Processos Quı́micos, Instituto

Nacional de Tecnologia, Av Venezuela 82, sala 518, Praça Mauá,

Rio de Janeiro, 20081-312, Rio de Janeiro, Brazil.

*Corresponding author(s). E-mail(s): [email protected];

[email protected];

Abstract
Sustainable development, where the materials need to be synthesized
and applied to their best performance, is the future. To gain insight
and deeply understand the relations between the structure and prop-
erties of the materials, computational studies have been consolidated
as a powerful tool. Therewith, periodic density functional calculations
were performed for the zirconium oxide (ZrO2 ). When it is applied as
a catalyst, the doping and vacancy effects of their crystalline phases
are important properties to guide new developments. This work inves-
tigates tetragonal and monoclinic crystalline phases of the Zn-doped
ZrO2 . Changes in the electronic and acid-basic properties were per-
formed by Bader charge analysis, the density of states calculations
(DOS) and the projected density of states (PDOS). The formation of

1
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2 Article Title

oxygen vacancies was also evaluated. The calculated oxygen vacancy

formation energies indicate that it is much easier to generate oxygen
vacancy in the Zn-doped ZrO2 than in the pure material. The most
stable material is the Zn-doped 3-fold coordinated Zr atom of the
m-ZrO2 , which can be used for future developments and applications.

Keywords: First Principles Calculations, Doping, Oxygen Vacancy,

Zn-doped ZrO2 , catalysis

1 Introduction
Zirconia oxide (ZrO2 ) is a material that has aroused great interest in the scien-
tific community for its general use in various technological applications, such
as fuel cells [1], solar cells [2], electronic devices [3], catalysis [4], dental bioma-
terial [5] and ceramics [6]. Within catalysis, studies of ZrO2 -based systems are
growing rapidly, either as support or as a catalyst. ZrO2 has three crystalline
phases (at atmospheric pressure): monoclinic (m-ZrO2 , < 1100 ◦ C), tetragonal
(t-ZrO2 , 1100 - 2370 ◦ C) and cubic (c-ZrO2 , > 2370 ◦ C) [7]. Its application as
a catalyst is highly related to its crystalline phases, with the tetragonal and
monoclinic phases being the most active[4]. Due to their acid-base properties,
ZrO2 and modified ZrO2 supported on metal catalysts have shown promising
results in methane reforming reactions [8]; hydrogenation of CO [9]; isobutane
and isobutene synthesis from gas conversion [10]; catalyzed alkylation, acy-
lation and isomerization reactions [11]; methanation reaction [12] and binary
and ternary system for producing methanol from CO/CO2 hydrogenation [13].
Doping ZrO2 with various transition metal ions or coupling other metal
oxides with different bandgaps (CeO2 , ZnO, SiO2 ) has attracted great atten-
tion to obtaining a better product than pure ZrO2 since the modified oxide
can greatly influence the physical, chemical, and electronic properties, pro-
viding high performance for catalytic activities [14–16]. This is an interesting
approach and has gained space, as it has shown improved physicochemical
properties, especially for photocatalytic activity [17] and sensors [18].
Recently, it has been reported that Zn doping in the ZrO2 induces the
formation of oxygen vacancies and, consequently, generates coordinatively
unsaturated Zr4+ sites (cus-Zr4+ ). These sites (oxygen vacancies and cus-Zr4+ )
can act as strong basic and acid sites, respectively [19]. Some authors have
invested in the butadiene synthesis from ethanol using the Zn-doped ZrO2 as a
catalyst[19, 20]. Chagas et al. [19] investigated the synthesis of butadiene from
ethanol. For this, they employed Znx Zr1−x O2−y type catalysts, using t-ZrO2
as a reference. They also observed that adding Zn into the t-ZrO2 was funda-
mental to promoting ethanol dehydrogenation and butadiene synthesis due to
the catalyst’s changes in the acidity and basicity because of the generation of
oxygen vacancies and cus-pairs during the reaction.
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Silva-Calpa and collaborators [21] showed that adding Zn to the ZrO2

can improve the redox properties of m-ZrO2 . The results displayed that
Znx Zr1−x O2−y catalysts were able to oxidize ethanol whereas m-ZrO2 was
not. In addition, the authors also verified that increasing the Zn concentra-
tion in the catalysts increases the CO2 conversion rate in the RWGS reaction.
They associated these results with the generation of O vacancies and the
improvement in O reducibility and mobility in the Znx Zr1−x O2−y catalysts.
Ticali et al. [22] studied bifunctional Zn-doped-ZrO2 /zeolite catalysts for
CO2 hydrogenation to methanol and conversion to value-added hydrocar-
bons. Three Zn-doped ZrO2 catalysts with the tetragonal crystalline structure
were prepared by co-precipitation (ZrZn-X, X = Zn wt%, i.e. 5, 15, 30).
The results showed that the amount of Zr4+ sites on the surface decreased
with increasing of Zn load while the number of oxygen vacancies increased.
The authors attribute this superior performance of the ZrZn-30 sample to
the higher amount of oxygen vacancies in the sample. Furthermore, through
Density Functional Theory (DFT) calculations they showed the presence of
Zn induces a stoichiometric oxygen vacancy, and the formation of additional
oxygen vacancies during activation is thermodynamically favored.
Chagas et al. [23] compared the properties of the two ZrO2 crystalline
phases most used in catalysis (tetragonal and monoclinic). They found that
the m-ZrO2 catalyst presents a higher number of weak and medium acid and
basic sites than t-ZrO2 , whereas t-ZrO2 exhibits a higher number of strong
acid sites. However, the density of strong basic sites of these two zirconia oxides
is similar. In this way, they concluded that the properties of the ZrO2 change
with the crystalline structure. Moreover, the authors found that t-ZrO2 is more
active in the Meerwein-Ponndorf-Verley reaction than m-ZrO2 .
Although Zn-doped ZrO2 have been investigated mostly from the viewpoint
of catalytic applications and their performance has surpassed pure ZrO2 , Zn-
ZrO2 thin films have shown excellent optical properties that make them of
great interest for optical and microelectronics technologies [24].
Both tetragonal and monoclinic crystalline phases of the Zn-doped ZrO2
present good catalytic, optical, and electronic properties. To evaluate the effect
of Zn dopant insertion on reactivity and oxygen vacancy formation in the ZrO2
bulk of monoclinic and tetragonal phases and compare them, we performed
ab initio calculations based on Density Functional Theory. Changes in the
electronic and acid-basic properties were investigated by Bader charge analysis,
the density of states calculations (DOS) and the projected density of states
(PDOS). The formation of oxygen vacancies was evaluated by calculating the
formation energies.

2 Computational Methods
All calculations were performed using the codes available in the Quantum
ESPRESSO package [25] which is based on the density functional the-
ory [26, 27] under periodic boundary conditions. The Kohn-Sham equations
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were solved with the Generalized Gradient Approximation (GGA) using the
Perdew-Burke-Ernzerhof exchange-correlation functional [28]. The core elec-
trons were represented with the projector augmented wave (PAW) method
[29]. Monkhorst-Pack [30] meshes of 5 x 5 x 3 and 6 x 6 x 6 k-point sampling
in the first Brillouin zone were used for t-ZrO2 and m-ZrO2 , respectively, in
order to obtain energy convergence of 2 x 10−5 eV/atom.
Considering that the standard DFT formulation usually fails to describe
strongly correlated electrons, which is corrected by the insertion of Hubbard U
parameter, the DFT+U methodology was implemented in this work [31]. It was
adopted U = 6.0 eV for the Zr d electrons, since this value correctly describes
the electronic structures of the oxidized and reduced zirconium oxide [32]. For
the Zn d electrons was used U = 5.0 eV [33]. Charge analysis was performed
via Bader method calculated by using the code developed by Henkelman and
co-worker [34].
Vacancies (VO ) were simulated by removing one oxygen atom from the
T-ZrO2 and m-ZrO2 bulks. The VO formation energy is defined as:

1
EF ormVO = Ecell − EO2 − Ecell–VO (1)
2

where Ecell is the total energy of the (doped or pure) zirconia bulk without
a vacancy, E(cell−VO ) is the total energy of the (doped or pure) zirconia bulk
with a vacancy and E(O2 ) is the calculated total energy for an O2 molecule
in the gas phase. To evaluate the stability of t-ZrO2 and m-ZrO2 materials
doped with a Zn atom, the formation energies were calculated according to
the following definition:

EF ormZn–ZrO2 = EZn–ZrO2 − EZrO2 + µZr − µZn (2)

in which EZn–ZrO2 and EZrO2 are the energies of doped and pure of the
t-ZrO2 and m-ZrO2 bulks, respectively, while µZr and µZn are the chemical
potentials of Zr and Zn atoms, respectively, calculated using the most stable
bulk phases. The magnitude of the interactions between the cations and the
anions of solids can be investigated by cohesion energy, Ecoh , obtained as:
P
Etotal−solid − Etotal−atom
atom
Ecoh = (3)
X
Etotal−solid and Etotal−atom are the total energies of the bulk and the atom,
respectively, and X is the number of cations in the solid.

3 Results and discussion

3.1 Pure m-ZrO2 and t-ZrO2 bulks
In the first step, we performed geometry optimizations for the two phases
of pure ZrO2 (m-ZrO2 and t-ZrO2 ) used in this work. Table 1 shows the
calculated lattice parameters, volume, cohesive energies of the m-ZrO2 and
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t-ZrO2 bulks, and experimental and theoretical data from the literature. A
good agreement can be seen between our results and values from previous
theoretical and experimental data. The relative error for the volume (in relation
to experimental data) was quite low (0.11%) for m-ZrO2 and low (5.96%) for
t-ZrO2 , and the relative error for the cohesive energies was 1.84% for the m-
ZrO2 and 6.69% for the t-ZrO2 , these values better than the calculated ones
from literature [35].

Table 1 Comparison between lattice parameters, volume, cohesive energies of the m-ZrO2
and t-ZrO2 bulk calculated in this work, and experimental and theoretical data from the
literature.

Lattice parameters/Å Volume (Veq /Å3 ) Ecoh /eV

a b c

This work 5.174 5.239 5.365 35.26 -23.27

Monoclinic Calc 5.1741 5.2391 5.3651 37.031 -24.641
Expt 5.1452 5.3102 5.3102 35.222 -22.853
This work 5.174 5.174 5.239 33.12 -24.23
Tetragonal Calc 5.1741 5.1741 5.2391 37.121 -26.201
Expt 5.1744 5.1744 5.239 35.224 -22.713

1 Reference [35]
2 Reference [36]
3 Reference [37]
4 Reference [38]

Before studying the effects of the Zn dopant, it is necessary to understand

the electronic structure of the pure m-ZrO2 and t-ZrO2 bulks. The calculated
Bader charges for the pure m-ZrO2 and t-ZrO2 bulks are presented in Figure 1.
The Bader charge analysis shows that Zn and O atoms of the t-ZrO2 bulk
have a higher charge than the m-ZrO2 bulk. Also, the charge of the 3-fold
oxygen atoms (-1.27e− ) of the m-ZrO2 bulk is lower than the charge of the
4-fold oxygen atoms (-1.32e− ).
The energy gap values obtained from DOS calculations were 5.80 for the
pure m-ZrO2 (which is in agreement with the values of other theoretical [39, 40]
and experimental [41, 42] works) and 5.65 eV for the t-ZrO2 bulks (which
is also very close to the theoretical and experimental values reported in the
literature [43, 44], Figure 2. That is, the monoclinic phase has a larger bandgap
than the tetragonal phase.
The acidity of a site can be analyzed by the conduction band (CB), the
projections closest to the Fermi level show the major tendency of the site to
receive electrons. On the other hand, the basicity of a site can be analyzed
by the valence band (VB), the projections closest to the Fermi level show
the major tendency of the site to donate electrons. The projections of the
PDOS calculations show that the valence band closest to the Fermi level of
both phase consists mainly of O 2p orbitals and the conduction band of Zr 3d
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Fig. 1 Bader charge (e− ) of (a) pure m-ZrO2 and (b) pure t-ZrO2 bulks. The green and
red spheres correspond to the Zr and O atoms, respectively.

orbitals, see Figure 2(a) and 2(b). This shows that the basic and acid sites of
these structures are the O and Zr atoms, respectively. Besides that, the VB
projections of the O 2p orbitals of t-ZrO2 are slightly closer to the Fermi level
than m-ZrO2 , indicating that the oxygen atoms of t-ZrO2 are slightly more
basic than the oxygen atoms of m-ZrO2 . On the other hand, the CB projections
of the Zr 2d orbitals of m-ZrO2 are slightly closer to the Fermi level than t-
ZrO2 , indicating that the zirconium atoms of m-ZrO2 are slightly more acid
than the zirconium atoms of t-ZrO2 .

Fig. 2 Total and projected densities of states of (a) pure m-ZrO2 and (b) pure t-ZrO2 bulks.
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3.2 m-Znx Zr1−x O2−y bulk

Doping was performed by replacing a Zr atom in the m-ZrO2 bulk with a Zn
atom. There are two types of Zr atoms in the monoclinic structure, one 3-fold
coordinated and the other 4-fold coordinated. Because of that, two different
models of doped m-ZrO2 were built. In the first model, the Zr atom substituted
by Zn is 3-fold coordinated, in the second, it is 4-fold coordinated, as shown in
Figure 3. The doped system was forced to maintain the monoclinic structure,
therefore, only atomic positions were optimized (lattice parameters were kept
fixed). The energies found for doping in the first and second models were
11.32 and 12.87 eV, respectively. These values show that the doping in 3-fold
coordinated Zn is more stable than 4-fold coordinated.

Fig. 3 Position of the Zn atom replacing the Zr atom (a) 3-fold coordinated and (b) 4-fold
coordinated. The grey and red spheres correspond to the Zn and O atoms, respectively.

As the structure of the first model is more stable, the vacancy formation
was done only using this structure. In this case, two models were also con-
structed. In the first model, the vacancy was generated by the removal of a
3-fold coordinated oxygen atom, in the second, 4-fold coordinated (Figure 4a
and b). The calculated oxygen vacancy formation energies in the first and sec-
ond models were 1.68 and 1.29 eV, respectively. This result indicates that it is
easier to generate an oxygen vacancy at the position of the 4-fold coordinated
oxygen atom.
To prove that the formation of stoichiometric oxygen vacancy is induced
by the presence of the Zn dopant, we also calculated the vacancy formation
energies in the pure m-ZrO2 . The calculated values were 5.42 and 5.29 eV for
the vacancy formation by the removal of a 3 and 4-fold coordinated oxygen
atom, respectively. Oxygen vacancy formation energies in the doped m-ZrO2
are much lower than in the pure m-ZrO2 . These results demonstrate that
the formation of oxygen vacancy is favored when the material is doped. This
explains the results observed in the experimental works that a greater number
of vacancies is formed when the m-ZrO2 is doped with Zn [19].
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Fig. 4 Electron localization function plot for the (a) 4-fold m-Znx Zr1−x O2−y and (b)
t-Znx Zr1−x O2−y .

The Electron Localization Function (ELF) plot reveals that there is no

electron density between the atoms, and the oxygen vacancy in the m-
Znx Zr1−x O2−y , which characterizes that the bonds between the atoms are
predominantly of ionic character. It can also be seen that the electrons remain
trapped in the oxygen vacancy. This observation is in agreement with the
results obtained by Ticali et al. [22] that verified the mono-ionization of the
trapped electrons in the oxygen vacancy (VO + ) .

Fig. 5 Bader charge (e− ) of (a) m-Znx Zr1−x O2−y with vacancy in the position of the 3-
fold coordinated oxygen atom, (b) m-Znx Zr1−x O2−y with vacancy in the position of the
4-fold coordinated oxygen atom, and (c) t-Znx Zr1−x O2−y systems. The green, grey and red
spheres correspond to the Zr, Zn and O atoms, respectively.

Figures 5(a-c) show the Bader charge analyses for m-Znx Zr1−x O2−y and
t-Znx Zr1−x O2−y systems, which indicate that the charges of the coordinately
unsaturated Zr atoms (Zr atoms neighboring the oxygen vacancy) are equal to
the charges of the regular Zr atoms in the lattice in the two cases (vacancy in
the position of the 3 and 4-fold coordinated oxygen atom). In the case of the
vacancy in the position of the 3-fold coordinated oxygen atom, the charges of
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the Zr atoms (+2.56e− ) are slightly lower than pure m-ZrO2 (+2.59e− ). The
charges of the 3 and 4-fold coordinated oxygen atoms decreased compared to
pure m-ZrO2 , Figure 1(a). The same behavior was observed for the charges
of the 3 and 4-fold coordinated oxygen atoms in the system with the vacancy
in the position of the 4-fold coordinated oxygen atom. However, in this case,
the charges of the Zr atoms (+2.65e− ) are greater than pure m-ZrO2 . The
charge of the Zn dopant in the system with the vacancy in the position of
the 3-fold coordinated oxygen atom is also slightly lower than in the system
with the vacancy at the position of the 4-fold coordinated oxygen atom. The
same behavior was observed for the charges of the oxygen atoms, that is, the
charges of the O atoms in the system with the vacancy at the position of the
3-fold coordinated oxygen atom are lower than in the system with the vacancy
at the position of the 4-fold coordinated oxygen atom. This shows that the
O atoms donate more electron density to the Zn and Zr atoms in the system
with the vacancy in the position of the 3-fold coordinated oxygen atom. These
results showed that the doping and the formation of the O vacancy cause local
electrostatic change. Doping m-ZrO2 and other similar metal oxides with 4d
and 5d metals can be very useful to adjust the electronic properties of these
metal oxides, which can be excellent candidates for photocatalytic processes,
optical properties, and microelectronics applications[45, 46].
The bandgap is reduced from 5.80 eV (pure m-ZrO2 ) to 2.61 eV (m-
Znx Zr1−x O2−y with oxygen vacancy at the position of the 3-fold coordinated
oxygen atom) and to 2.40 eV (m-Znx Zr1−x O2−y with oxygen vacancy at the
position of the 4-fold coordinated oxygen atom). These results are in agree-
ment with experimental results [47]. As the bandgap of the m-ZrO2 decreases
with the insertion of Zn dopant, and with the oxygen vacancy formation, one
can say that more electrons may be excited from the valence band to the
conduction band, which increases the electrical conductivity of the Zn-doped
m-ZrO2 [47].
The projections from PDOS calculations displayed in Figures 6(a) and 6(b)
show that the conduction band of the m-Znx Zr1−x O2−y compound closest to
the Fermi level consists of Zn 4s orbitals and cus-Zr4+ 3d orbitals. Besides
that, Figures 6(a) and 6(b) indicate that the projections of the cus-Zr4+ 3d
orbitals shift closer to the Fermi level in the CB in the m-Znx Zr1−x O2−y in
relation to the Zr4+ 3d orbitals pure m-ZrO2 (Figures 2(a)). This suggests
that the cus-Zr4+ atoms are more acid than the regular lattice Zr4+ atoms,
i.e., they are more reactive.
Comparing the acidity of the cus-Zr and the dopant, Figure 6(a) indicates
that when the vacancy is generated at the position of the 3-fold coordinated
oxygen atom it creates cus-Zr4+ sites more acids than the Zn dopant. When
the vacancy is generated at the position of the 4-fold coordinated oxygen atom,
the cus-Zr4+ sites and the Zn dopant have similar acidity.
Figures 7(a) and 7(b) suggest that the contributions of the oxygen atoms
bonded and non-bonded to the dopant are similar close to the Fermi level in
the VB of m-Znx Zr 1−x O2−y . Furthermore, Figures 7(a) and 7(b) show that
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the projections of the 2p orbitals of the 3 and 4-fold coordinate oxygen atoms
shift closer to the Fermi level in the valence band in the m-Znx Zr1−x O2−y in
relation to the pure m-ZrO2 . This result shows that the 3 and 4-fold coordinate
oxygen atoms in the m-Znx Zr 1−x O2−y are more basic than oxygen atoms in
the pure m-ZrO2 . Therefore, these oxygen atoms are more reactive than the
oxygen atoms in the pure m-ZrO2 .

Fig. 6 Total and projected densities of states of Zr e Zn atoms (a) m-Znx Zr1−x O2−y with
vacancy in the position of the 3-fold coordinated oxygen atom, (b) m-Znx Zr1−x O2−y with
vacancy in the position of the 4-fold coordinated oxygen atom, and (c) t-Znx Zr1−x O2−y
systems.

Fig. 7 Total and projected densities of states of O atoms (a) m-Znx Zr1−x O2−y with the
vacancy in the position of the 3-fold coordinated oxygen atom, (b) m-Znx Zr1−x O2−y with
the vacancy in the position of the 4-fold coordinated oxygen atom, and (c) t-Znx Zr1−x O2−y
systems. In the m-Znx Zr1−x O2−y with the vacancy in the position of the 4-fold coordinated
oxygen atom there are only 3-fold coordinated oxygen atoms non-bonded to the dopant.

3.3 t-Znx Zr1−x O2−y bulk

As performed for the m-Znx Zr1−x O2−y system, the doping in the t-
Znx Zr1−x O2−y system was carried out by replacing a Zr atom in the t-ZrO2
bulk with a Zn atom. The doped system was forced to maintain the tetragonal
structure, therefore, only atomic positions were optimized (lattice parameters
were kept fixed). The calculated energy for doping was 11.56 eV. This result
shows that the doping on the t-ZrO2 is more stable than doping on the 4-fold
coordinated Zr atom of the m-ZrO2 , but less stable than doping on the 3-fold
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coordinated Zr atom of the m-ZrO2 . Therefore, depending on where the dop-

ing occurs, it may be easier or not promoting the doping of m-ZrO2 bulk in
relation to the t-ZrO2 bulk, which demonstrates the powerful of theoretical
calculations on designing new materials or, at least, propose modifications into
the current materials.
The calculated oxygen vacancy formation energy was 1.82 eV. In the same
way as done for m-ZrO2 , we also calculate the vacancy formation energy in the
pure t-ZrO2 for comparison. The value found was 8.20 eV. This value is much
higher than that for the t-Znx Zr1−x O2−y . This result demonstrates that the
formation of oxygen vacancy is favored by the presence of the Zn dopant. This
explains the results observed in the experimental works that a greater number
of vacancies is formed when the t-ZrO2 is doped with Zn [19]. Comparing the
values obtained for pure t-ZrO2 and t-Znx Zr1−x O2−y with the values obtained
for the m-ZrO2 and m-Znx Zr1−x O2−y , it is observed that the formation of
oxygen vacancy is favored in the monoclinic phase.
The Electron localization function (ELF) plot (Figure 4(b)) indicates that
there is also no electron localization between atoms and the oxygen vacancy
in the t-Znx Zr1−x O2−y . Therefore, the bonds between the atoms in the t-
Znx Zr1−x O2−y are also predominantly of ionic character and the electrons
remain trapped in the oxygen vacancy.
Figure 5(b) shows that the charge Zr atoms decreases from -2.86e− in the
pure t-ZrO2 (Figure 1(b)) to +2.47e− in the t-Znx Zr1−x O2−y . Moreover, the
charges of the coordinately unsaturated Zr atoms are the same as the regular
Zn atoms in the lattice. The charge of the oxygen atoms neighboring to the
Zn dopant decreases from -1.43e− in the pure t-ZrO2 to -1.19e− in the t-
Znx Zr1−x O2−y , and the charge of the other oxygen atoms remained close to
the charge of pure t-ZrO2 . The charge of the Zn dopant in t-Znx Zr1−x O2−y is
lower than in m-Znx Zr1−x O2−y . It was also verified a greater reduction in the
charges of the oxygen atoms neighboring the vacancy in the t-Znx Zr1−x O2−y
(in relation to the pure) than in the m-Znx Zr1−x O2−y . This suggests that
the O atoms donate more electron density to the Zn and Zr atoms in the t-
Znx Zr1−x O2−y than in the m-Znx Zr1−x O2−y . These results showed that the
doping and the formation of the O vacancy also cause a local electrostatic
change in the t-Znx Zr1−x O2−y system.
The bandgap is reduced from 5.65 eV (pure t-ZrO2 ) to 1.04 eV (t-
Znx Zr1−x O2−y ). This reduction was also observed in experimental works [48,
49]. As observed for the monoclinic system, the CB of the t-Znx Zr1−x O2−y
compound closest to the Fermi level consists of Zn 4s orbitals and cus-Zr4+ 3d
orbitals (Figures 6(c)). The projections of the cus-Zr4+ 3d orbitals also shift
closer to the Fermi level in the CB in the t-Znx Zr1−x O2−y in relation to the
Zr4+ 3d orbitals pure t-ZrO2 (Figures 2(b)). This suggests that the cus-Zr4+
atoms are more acid than the regular lattice Zr4+ atoms, i.e., they are more
reactive. Unlike the monoclinic system, the acidity of the dopant is higher than
that of the cus-Zr sites.
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Figure 7(c) shows that the projections of the O 2p orbitals shift closer to
the Fermi level in the valence band in the t-Znx Zr1−x O2−y in relation to the
pure t-ZrO2 . This demonstrates that the oxygen atoms in the t-Znx Zr 1−x O2−y
are more basic than oxygen atoms in the pure t-ZrO2 . Then the oxygen atoms
in the t-Znx Zr1−x O2−y are more reactive than the oxygen atoms in the pure
t-ZrO2 . Besides that, Figure 7(c) shows that the contributions of the oxygen
atoms bonded to the dopant are closer to the Fermi level in the VB of t-
Znx Zr 1−x O2−y compound than those non-bonded to the dopant. Therefore,
the oxygen atoms bonded to the dopant are less basic. This is in line with the
Bader charge, Figure 5(b). These atoms have a lower negative charge, that is,
they are less likely to donate electrons.
Figures 6 and 7 indicate that the oxygen atoms of the t-Znx Zr1−x O2−y
compound have similar basicity to the atoms of the m-Znx Zr1−x O2−y com-
pound, but the cus-Zr4+ sites and Zn dopant are slightly more acid than ones
of the m-Znx Zr1−x O2−y when the vacancy is generated at the position of the
3-fold coordinated oxygen atom and it is similar when the vacancy generated
at the position of the 4-fold coordinated oxygen atom.

4 Conclusion
Ab initio calculations based on DFT were used to investigate the effect of Zn
dopant insertion on reactivity and oxygen vacancy formation in the ZrO2 bulk
of monoclinic and tetragonal crystalline phases.
The calculated oxygen vacancy formation energies indicate that it is much
easier to generate oxygen vacancy in the Zn-doped ZrO2 than in the neat
material for both phases. Besides that, oxygen vacancy formation is favored
in the monoclinic phase.
Electron localization function analysis showed that the electrons remain
trapped in the generated oxygen vacancy for both phases. On the other hand,
the density of states revealed a large reduction in the bandgap value from pure
ZrO2 to Zn-doped ZrO2 systems.
The doping on the t-ZrO2 was more stable than doping on the 4-fold
coordinated Zr atom of the m-ZrO2 but less stable than doping on the 3-
fold coordinated Zr atom of the m-ZrO2 , highlighting the importance of the
obtained results on guiding new experiments. Bader charge analyses and pro-
jected density of states indicated that the doping of ZrO2 with Zn creates more
basic sites (oxygen atoms). The results demonstrate that the oxygen atoms
of the t-Znx Zr1−x O2−y system have similar basicity to the atoms of the m-
Znx Zr1−x O2−y system, but the cus-Zr4+ sites and Zn dopant are slightly more
acid than ones of the m-Znx Zr1−x O2−y .
These results improve the understanding of the Zn-doping effect in the
ZrO2 bulk and the formation of oxygen vacancies in both crystalline phases
to design new materials with customized properties and high performance in
various applications.
 Springer Nature 2021 LATEX template

Article Title 13

Supplementary information. All input files and optimized structures for

each system are shared as free of charge in the Supporting Material.
Acknowledgments. The authors acknowledge the financial support from
FAPERJ, CAPES and CNPq. R. C. Mancera and L. T. Costa thanks for
the Computing Resources from OSCAR and CENAPAD Server. Luciano
T. Costa also acknowledges the support from PRINT-CAPES-UFF and
CAPES/STINT projects (Grant Numbers 17846692372, CAPES/PRINT
1038152P and 88881.465529/2019-01)

Declarations
ˆ Funding Rafael C. Mancera reports financial support was provided by
CAPES, Luciano T Costa reports financial support was provided by
National Council for Scientific and Technological Development.
ˆ Conflict of interest The authors declare no competing interests.
ˆ Ethics approval N/A
ˆ Consent to participate N/A
ˆ Consent for publication N/A
ˆ Availability of data and materials N/A
ˆ Code availability N/A
ˆ Authors’ contributions: Rafael C. Mancera: Investigation, Methodology,
Validation, Writing - Original Draft; Viviane S. Vaiss: Writing - Review,
Supervision; R. R de Avillez: Conceptualization, Writing - Review; Lucia
Appel: Conceptualization, Writing - Review; Luciano T. Costa: Fund-
ing Acquisition, Project Administration, Supervision, Writing – Review and
Editing, Resources, Conceptualization.

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