Density Functional Theory (DFT) Analysis of the

Oxygen Vacancies of TiO2 for Improving

its Photocatalytic Functions

by

Christian Joshua N. Lee

Cherine Fates L. Mangulabnan

A Thesis Proposal Submitted to the

School of Chemical, Biological, and Materials Engineering and Sciences
in Partial Fulfillment of the Requirements for the Degree

Bachelor of Science in Chemical Engineering

Mapúa University
August 2021
 TABLE OF CONTENTS

TITLE PAGE i

APPROVAL PAGE ii

ACKNOWLEDGMENT iii

TABLE OF CONTENTS iv

LIST OF TABLES v

LIST OF FIGURES vi

Chapter 1: INTRODUCTION 1

Chapter 2: REVIEW OF LITERATURE 3

1. Photocatalytic Reaction of TiO2 3

2. Analysis on the structure of TiO2 and its effect 6
3. O-vacancy of Titanium Dioxide 7
4. Application of Density Functional Theory 9

OXYGEN VACANCY ANALYSIS ON ANATASE TiO 2 12

1. Methodology 12

REFERENCES 16

ii
 LIST OF TABLES

Chapter 2
TABLE 1: Different Semiconductors and their band gaps 3

OXYGEN VACANCY ANALYSIS ON ANATASE TiO 2

TABLE 1: Crystallographic properties of TiO2 12

iii
 LIST OF FIGURES

Chapter 2
FIGURE 1: TiO2 applications as photocatalyst 4
FIGURE 2: Degradation of organic pollutants 5
FIGURE 3: Crystalline structures of (a) R-TiO2, (b) A-TiO2 and (c) B-TiO2 6
FIGURE 4: The optimized configurations (top view) of pristine TiO2 (c1) and OVs- 10
TiO2 (c2) based on the DFT calculations

OXYGEN VACANCY ANALYSIS ON ANATASE TiO 2

FIGURE 1: Flow diagram of the methodology 13
FIGURE 2: Crystalline structure of Anatase TiO2 14

iv
 Chapter 1

INTRODUCTION

Titanium dioxide (TiO ) has been considered in the photocatalytic

2

technology as a semiconductor with such advantages like high stability, non-toxic

and high photocatalytic activity. A photocatalytic process substantially converts

solar energy into chemical energy like the reduction of pollutants or removal of

toxic compounds [1]. The efficiency of TiO as a photocatalyst has become

2

prominent due to its low cost, wide source and safety to the environment and

humans [2]. However, its relatively wide bandgap greatly limits its efficiency and

results in unsatisfactory photocatalytic performance [3]. TiO could not reach its
2

peak performance due to low light capability, and high recombination rate [4] that

limits its widespread application particularly for anatase TiO [5].

2

Structural defects pose a challenge in various energy conversion

technologies. Such defects are caused by oxygen vacancies (OVs) formed when an

oxygen atom is eliminated from the lattice and significantly affect the

photocatalytic performance [6]. As a result, many efforts have been conducted to

improve the performance of TiO in applications. Various techniques have been

2

done in enhancing the photoefficiency of TiO such as doping it with different

2

metals [7], simple hydrogenation process [5], codoping [8], etc.

Strategies for the synthesis of defective TiO with oxygen vacancies have
2

been investigated whereas the importance of OVs has been recognized. However,

1
 earlier studies centered on the reaction mechanism of the photocatalytic reactions

while the observation of oxygen vacancies remains largely unexplored [4].

This study seeks to measure the oxygen vacancies of TiO for the 2

photocatalytic reaction using the density functional theory (DFT). We are to

measure the effect of OVs on the overall photocatalytic performance correlated with

computational analysis and identify the energy potential of TiO . Since oxygen
2

vacancy contributes to the photo efficiency of TiO by generating electron-rich

2

active sites, this study will focus on the analysis of the computational description of

oxygen vacancies in TiO under the parameters available to DFT. The CP2K
2

software will simulate our DFT calculations.

Many studies have been done to further improve the photocatalytic activities

specifically in nitrogen monoxide (NO) removal. Studies that directly investigate

the impact of these OVs have been relatively constrained and are often

contradictory, thereby limiting our understanding of the TiO photocatalytic

2

performance [6]. Therefore, it is significant to analyze the oxygen vacancies of TiO 2

to reduce the wide bandgap energy. The results of this study could potentially serve

as a guide for future studies in this field. 

The present work will focus on the utilization of TiO 2 as a photocatalyst. It will be

limited to the optimization of the photocatalytic reaction of TiO 2 with oxygen vacancy. The

unit cell of Anatase will be used for this study. A computational method will be done to

investigate the effect of the oxygen vacancies on the photocatalytic performance TiO 2 . The

2
results of this study can be validated through an experimental validation system. However, in

our case, the study will be validated based on literature studies.

3
 Chapter 2

REVIEW OF LITERATURE

1.     Photocatalytic Reaction of TiO2

Titanium Dioxide as photocatalyst and its applications

Titanium dioxide (TiO2) is a semiconductor which is predominantly utilized for its

photocatalytic properties which can be potentially used for clean energy production and

environmental solution [8]. The vast majority of researchers have explored the mechanism

involved within the photocatalytic performance of semiconductors such as TiO 2 [2]. However,

Li et al stated that TiO2 does not meet the ideal photocatalytic activity because of its weak

absorption capability and high recombination rate of electron-hole pairs [9]. As shown in

Table 1, since TiO2 has a wide bandgap of 3.20 eV [1,8], it is active only under ultraviolet

(UV) irradiation [3].

Table 1. Different Semiconductors and their band gaps [8].

Semiconductor Band Gap (eV at 300K)
ZnS (Wurtzite) 3.91
ZnS (Zinc blende) 3.54
SnO2 3.60
TiO2 3.20
ZnO 3.03
WO3 2.60
CdS 2.42
Fe2O3 2.20
CdO 2.10
Cu2O 2.10
CdSe 1.70
AlSb 1.58
CdTe 1.56
GaAs 1.42

4
 A photocatalytic reaction is a widely used process due to its moderate reaction

condition, low cost, and benefits for the environment [9][10]. Photocatalysts are

stable, non-toxic, and cheap which are largely applied for antifouling, antifogging,

conservation of energy, deodorization, sterilization, self-cleaning, air and water

treatment, etc (Fig.1) [8]. Notably, TiO2 has non-toxic properties that can be very

helpful when using it as a photocatalyst [1].

Figure 1. TiO2 applications as photocatalyst [1].

TiO2 is often stated as photonic efficiency which exhibits low quantum yields [11]. Due to

the low light utilization and wide bandgap of TiO2 [5], its widespread application was

restricted for application [12]. To this point, the use of titanium dioxide has been limited.

Many studies have conducted modifications to enhance the performance of TiO 2 [8,9].

Various techniques in improving visible-light response and controlling the strong

recombination rate in TiO2 have been explored, such as making TiO 2 colorful through metal or

non-metal doping [5], modification of TiO2 surface with metals [12], and hydrogenation of

5
TiO2 [7]. In order to enhance the photocatalytic process of TiO 2, it has been extensively

studied for the removal of several pollutants (Fig. 2) on various approaches such as the sol-gel

method [5], spin coating method, pulsed laser deposition method, etc [1]. Additionally,

methods like limiting the bandgap, reducing of recombination rate, and enhancing adsorption

ability can also increase the photocatalytic performance of TiO2 [2].

Figure 2. Degradation of organic pollutants [8].

In earlier work, TiO2 was studied as the photocatalyst for the removal of NO from the air

[13]. Trapalis et al observed the photocatalytic activity of TiO 2 in NOx removal. In their

findings, the bandgap difference of graphene ssG and graphene rGO resulted in different

photocatalytic behaviors of TiO2/G and TiO2/rGO materials [2].

Meanwhile, Wodka (2010) used TiO2 for the removal of organic impurities from water.

Since TiO2 has high physical and chemical stability, it oxidized the organic pollutants upon

UV exposure [12] into nontoxic compounds. Also, TiO2 is a transition metal oxide suitable for

multiple applications in optoelectronics and photoelectrochemistry [14]. Because of its optical

6
transparency, catalytic activity, and electrochemical stability, researchers have explored the

photocatalytic activity of TiO2. 

2.     Analysis on the structures of TiO2 and its effect

Knez et al indicated that titanium dioxide crystallizes into three such as anatase, rutile, or

brookite polymorph [14]. The structures of TiO2 in Fig. 3 would be crucial in the performance

of the compound as a photocatalyst. Different structures of the compound might affect certain

properties of the compound when undergoing the said process. These mineral forms have a

crystalline structure of tetragonal (anatase and rutile) and orthorhombic (brookite) [1]. Earlier

work examined a modified TiO2 under UV-visible light for its photocatalytic performance and

yielded a high photooxidation compared with pristine TiO2 [7].

(a)                                           (b)                                 (c)

Figure 3. Crystalline structures of (a) R-TiO2, (b) A-TiO2 and (c) B-TiO2 [1].

It is noticeable that Anatase TiO2 is dipyramidal in structure (Fig.3b) while Rutile phase

TiO2 is prismatic (Fig. 3a) [1]. Anatase TiO2 presents dominant photocatalytic performance as

compared to rutile and brookite (Fig. 3c) due to its unique photoactivity [15]. Even though

anatase is known for its indirect optical band gap of 3.2 eV, it remains the ideal configuration

7
for applications. Its electronic properties are largely determined by the presence of excess

electrons [14].

The study of Trapalis et al (2016) analyzed that limiting the bandgap of TiO 2 and reducing

the rate of recombination of electron-hole pairs can improve the efficiency of anatase TiO 2.

Since the mechanism of a semiconductor refers to its ability to create electron–hole pairs with

light, the required energy to form electron-hole pairs depends on the energy gap of the

semiconductor [2].

3.     O-vacancy of Titanium Dioxide

Effect on the Photocatalytic Performance of TiO2

OVs have been widely used to enhance the performance of photocatalysts [16]. The

deficiency contributes to the photo efficacy of TiO2 by producing electron-rich active sites

[17]. Similarly, Hinuma et al observed that the formation of electrons in the surface defect

affects the catalytic performance of metal oxide [4]. It usually generates shallow sub-band-gap

states responsible for n-type doping and device performance [6]. Elavarasan et al discussed

that oxygen deficiencies can modify the disordering oxygen vacancies. Furthermore, it was

found that poor oxygen conditions result in interstitial and intrinsic defects [7].

In the work of Zhao et al, OVs showed a dominant effect in the photocatalytic NO

removal process where the rise of temperature affected the catalytic performance [18]. This

study coincides with the study of Li et al which states that OVs can promote the removal of

NO. They have found that operating at high temperatures would change the phases of TiO 2,

particularly anatase to rutile [9]. As a result, the OVs of TiO 2 could be adjusted by changing

8
the calcination temperature [9]. Furthermore, Li et al also revealed that a suitable amount of

OVs in catalyst leads to the accumulation of electrons in o-vacancy. It enhanced the

photocatalytic activity of TiO2 when electrons reacted with H2O2 and NO under UV light [9].

As eloquently stated by Knez et al, OV has the ability to regulate the physical properties

and technical applications of TiO2 [14]. Fundamentally, it is present in anatase TiO2. OVs

develop the light absorption and expand the concentration of bulk carriers. These defects can

induce detrimental structural and phase changes and have been reported to act as

recombination centers that lower quantum yields [6].

Hinuma et al mentioned that surface OV is a parameter which recognizes the catalytic

performance of metal oxides like titanium dioxide [15]. Statistical investigations indicate that

the band gap, bulk formation energy, and electron affinity are factors that strongly influence

oxygen vacancy energy [4]. Band gap refers to the difference in energy between the valence

gap and the conduction band [8]. When electrons enter defect states after O desorption, these

states can either be in valence band, mid-gap, or in the conduction band [4].

Forming in-gap states by OV will expand the photocatalytic activity of the material within

the range of light [14]. Notably, it modifies the morphology, structure, electrical and optical

properties of a semiconductor which affects its light absorbance, charge-carrier mobility,

redox potential, and surface area [8]. Based on the study of Ameta et al (2018), it has been

identified that such a wide band gap makes a crystalline metal oxide such as Titania to be

active under UV range. Note that in their study, formation of mid-gap states induced an

energy gap in titania when synthesizing it with a solution phase method. Furthermore,

9
undoped mixed-phase TiO2 nanoparticles achieve the band gap of about 2.2 eV and possess

oxygen vacancy and high surface area, accelerating its photo reactivity [8].

In the recent work of Bi et al, the OV content in the TiO 2 of their three samples such as (1)

white TiO2 (W-TiO2), (2) gray TiO2 (G-TiO2) and (3) black TiO2 (B-TiO2) and its relationship

to the photocatalytic performance have been explored. It has been found that energy bandgap

of G-TiO2 and B-TiO2 is tuned from 3.10 to 3.02 and 1.99 eV and the content of oxygen

vacancy is 1%, 4.8% and 7.8% for W-TiO 2, G-TiO2 and B-TiO2, respectively. The results

were significant for the design of high-performance photocatalytic materials in the field of

solar energy [5].

Additionally, black TiO2 was synthesized by Li et al. at different temperatures of N 2 and

compared it with TiO2 calcined in air. Due to the oxygen vacancies in black TiO 2, the catalytic

performance of black TiO2 was better than TiO2 calcined in air [9]. Similarly, a simple

hydrogenation process was done to black TiO2, which resulted in visible light absorption. This

is because of the formation of oxygen vacancy, and new band level wherein the lowest value

of band gap (1.54 eV) exhibited absorbance of light even in the near-infrared region [5].

4. Application of Density Functional Theory

Heterogeneous fluids with cohesive structure are commonly studied using the density

functional theory (DFT). It encompasses thorough concepts used in molecular simulations

along with the adaptable equations of state employed to study the behavior of fluids [19]. It is

was previously used to further understand the electronic structure of OVs-TiO2 [3].

10
 In the work of Elahifard et al, it was suggested that DFT subsurface positions are more

favorable where o-vacancies cannot diffuse to the surface of anatase [17]. Their findings

showed that oxygen deficiency had similar results on the structures of anatase and rutile.

However, the charge distributions presented a difference while the transferred charge from

two defects were localized on three nearest Ti atoms in rutile. Furthermore, the defect

positions disperse their charges independently in anatase phase [17].

Figure 4. The optimized configurations (top view) of pristine TiO2 (c1) and OVs-TiO2

(c2) based on the DFT calculations [3].

Additionally, the DFT method focuses on the substantial properties. It was used to

evaluate the O2 and NO adsorption on the surface of TiO 2 and OVs-TiO2, correspondingly [3].

The DFT calculations showed the OVs energy formation as an effect of carbon-doping. It was

known that after the calcination process, carbon elements could not reain due to the increase

in the formation energies of OVs. Figure 4 demonstrates the difference on the optimized

structures of TiO2 (Fig. 4 c1) and OVs-TiO 2-N2 (Fig. 4 c2). Compared with TiO 2, the OVs-

TiO2-N2 showed distinctive lattice deformation as calculated using DFT [3].

11
 Moreover, previous literature utilized a hybrid functional or a DFT+U approach which

recovered the antiferromagnetic of reduced anatase, a band gap greater than 3 eV, and gap

states ∼1 eV below the conduction band found in the experiment [15]. Additionally, Jia, R.

and Wang, Y. proved that through the calculation of DFT, OVs in titanium oxide weakens the

bond between N-O which results in the prevention of more unwanted byproducts formation

and high efficiency of removal of NO [16].

12
 X
OXYGEN VACANCY ANALYSIS ON ANATASE TiO2

1. Methodology

1.1 Characterization

Among the phases of TiO2, rutile and anatase are prominently used. To further

understand the structural properties of the TiO2, DFT calculations will be carried

out. Anatase phase has tetragonal structure with the space group of 141− I41/amd as

shown in Table 1. The standard setting of space group number will indicate the

surface orientation of the phase [4]. In reference to the work of Hinuma et al, the

optimized lattice constants of the bulk structures for rutile phase are a = b = 4.639 Å

and c = 3.001 Å while a = b = 3.858 Å and c = 9.557 Å for anatase phase [4].

However, the lattice constants that will be utilized for Anatase will be obtained

from Table 1. The supercell to be used is 2 × 2 × 1 for anatase in perfect and

defective states [17].

The total energy, crystal configuration, band structure and partial density of

orbitals (PDOS) are to be measured based on DFT with the generalized gradient

13
 approximation (GGA) [17]. In order to identify which atomic configuration is

much stable, the first-principle calculations using full potential periodic DFT and

GGA will be done [4].

Table 1. Crystallographic properties of TiO2 [1].

Properties Rutile Anatase Brookite
Crystal Structures Tetragonal Tetragonal Orthorhombic
Lattice constants (A°) a = 4.5936 a = 3.784 a = 9.184, b = 5.447
c = 2.9587 c = 9.515 c = 51.54
Molecule (cell) 2 2 4
Space groups P42/mnm I41/amd Pbca
Volume/molecule 31.2160 34.061 32.172
Density (g/cm3) 4.13 3.79 3.99
O-Ti-O bond angle 81.2° 77.7° 77.0°-105°
90.2° 92.6°
1.2 Computational Method

To study the effects of OVs in the TiO2, a software from CP2K will serve as our

simulator for our DFT calculations. The crystalline structure of Anatase TiO 2 will

be used for our simulations. Aside from the software, we would also use a third-

party software to accompany CP2K for our graphical user interface since CP2K

software does not have any graphical input or output validation. For the structure of

anatase TiO2, we would have it imported from an online database.

Download the structure ofInput thethe

Import
Anatase code
TiO2.required
structure of for
the the simulation.
TiO2.in Remove
the third oxygen bonds in the structure for oxygen
party software.

Export the file to CP2K for the simulation process.

ad the simulated file and import it to the third party software for the reading of the results.

Repeat all the process with the different oxygen vacancies TiO2.

14
 Figure 1. Flow diagram of the methodology.

For the first step of the methodolody as illustrated in Figure 1, we are to find a

crystalline structure of Anatase that would be used throughout the study. The file of

the structure will be entered to our third party software which is our input and

output interface for this simulation. Then, we will remove the oxygen bonds in the

structure (Fig. 2) which will signify our OVs in anatase structure. Afterwards, NO

will be added near the oxygen vacancies to simulate the absorption of the NO in

TiO2. Then, we shall proceed to exporting the file to the CP2K simulator to

calculate for the energy of formation in the OVs. After the simulation, we would

import back the file into our third party software to read the output data and show

the energy of formation of our OV with NO. Lastly, the process will be repeated

from the removal of oxygen bonds in our structure. This will show the different

band gap energy of formation at different OVs of the anatase structure.

15
 Figure 2. Crystalline structure of Anatase TiO2.

To study the effects of OVs on the structure partial density of states (pDOS), it

will be calculated using the hybrid function particularly Heyd-Scuseria-Emzerhof

(HSE) to enhance the accuracy of defect states particularly for band gaps. The use

of HSE will explore the effect of enhancing the OV concentration and its

interactions with the TiO2 super cells. Ha et al’s values of HSE functional with 25%

Hartree−Fock (HF) exchange and a screening parameter of ω = 0.200 bohr−1 will

be tested [15]. Furthermore, the grid of 18 × 18 × 6 k-points for anatase will be

applied for integrating the first Brillouin zone during density of states (DOS)

calculations. The OV formation energy is defined as:

(1)

16
where refers to the energy of the slab with no defects, the energy of the

constituents of the slab in a perfect bulk and the energy of the slab when two O atoms are

removed from each surface. The parameter is the chemical potential of the O which is

half of the total energy of an isolated oxygen molecule. O is the removed atom wherein the

chemical potential pertains to O2 gas in the current case [4].

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