QUANTUM MECHANICAL INVESTIGATION OF CO OXIDATION

CONDUCTED ON AUTOMOTIVE EXHAUST EMISSION CATALYSTS

CONTAINING LA AND PD/LA ON CERIA-ZIRCONIA

A THESIS SUBMITTED TO
THE GRADUATE SCHOOL OF NATURAL AND APPLIED SCIENCES
OF
MIDDLE EAST TECHNICAL UNIVERSITY

BY

YASEMİN KAYA

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR
THE DEGREE OF MASTER OF SCIENCE
IN
CHEMICAL ENGINEERING

JANUARY 2016
 Approval of the thesis:

QUANTUM MECHANICAL INVESTIGATION OF CO OXIDATION

CONDUCTED ON AUTOMOTIVE EXHAUST EMISSION CATALYSTS
CONTAINING LA AND PD/LA ON CERIA-ZIRCONIA

submitted by YASEMİN KAYA in partial fulfillment of the requirements for the

degree of Master of Science in Chemical Engineering Department, Middle
East Technical University by,

Prof. Dr. Gülbin Dural ________________

Dean, Graduate School of Natural and Applied Sciences

Prof. Dr. Halil Kalıpçılar ________________

Head of Department, Chemical Engineering

Prof. Dr. Işık Önal ________________

Supervisor, Chemical Engineering Dept., METU

Examining Committee Members:

Prof. Dr. İnci Eroğlu ________________

Chemical Engineering Dept., METU

Prof. Dr. Işık Önal ________________

Chemical Engineering Dept., METU

Assoc. Prof. Dr. Mehmet Ferdi Fellah ________________

Chemical Engineering Dept., BTU

Assoc. Prof. Dr. Görkem Külah ________________

Chemical Engineering Dept., METU

Assist. Prof. Dr. Erhan Bat ________________

Chemical Engineering Dept., METU

Date: 26.01.2016
I hereby declare that all information in this document has been obtained and
presented in accordance with academic rules and ethical conduct. I also
declare that, as required by these rules and conduct, I have fully cited and
referenced all material and results that are not original to this work.

Name, Last name : Yasemin Kaya

Signature :

iv
 ABSTRACT

QUANTUM MECHANICAL INVESTIGATION OF CO OXIDATION

CONDUCTED ON AUTOMOTIVE EXHAUST EMISSION CATALYSTS
CONTAINING LA AND PD/LA ON CERIA-ZIRCONIA

Kaya, Yasemin

M.Sc., Department of Chemical Engineering

Supervisor: Prof. Dr. Işık Önal

January 2016, 55 pages

In this study, Three Way Catalyst (TWC) is investigated via Density Functional
Theory (DFT) methods. DFT techniques are implemented by Vienna Ab Initio
Simulation Package (VASP). Atomic lanthanum substituted and both palladium
and lanthanum substituted CZO (110) surfaces are investigated for their catalytic
activity in terms of carbon monoxide oxidation. Relative energy profiles for CO
reaction mechanisms on these surfaces are obtained and activation barriers of
reaction steps are analyzed by using CI-NEB method. It is observed that Oxygen
Storage Capacity (OSC) of CZO is remarkably enhanced by the introduction of
lanthanum to CZO and Pd-CZO structure. The catalytic activity on La-doped
surface in terms of CO oxidation is found as energetically more favorable

v
compared to Pd+La doped surface since there is no activation barrier for the
reaction steps carried out on this surface.

Keywords: Three Way Catalytic Converters, Ceria-Zirconia, Carbon Monoxide

Oxidation, Density Functional Theory, Computational Chemistry

vi
 ÖZ

LA VE PD/LA İÇEREN SERYUM-ZİRKONYUM OKSİT OTOMOTİV

KATALİZÖRLERİ ÜZERİNDE CO OKSİDASYONUNUN KUANTUM
MEKANİKSEL ÇALIŞMASI

Kaya, Yasemin

Yüksek Lisans, Kimya Mühendisliği Bölümü

Tez Yöneticisi: Prof. Dr. Işık Önal

Ocak 2016, 55 sayfa

Bu çalışmada, Üç Yollu Katalizör (TWC) Yoğunluk Fonksiyonel Teorisi (DFT)

yöntemi kullanılarak incelenmiştir. DFT teknikleri Viyana Ab İnitio Simülasyon
Paketi (VASP) yolu ile uygulanmıştır. Atomik lantan ve paladyum ile lantan
birlikte yerleştirilmiş seryum-zirkonyum oksit (CZO) (110) yüzeylerin, karbon
monoksit oksidasyonu açısından katalitik aktivitesi incelenmiştir. CO oksidasyon
reaksiyon mekanizması için göreli enerji profilleri elde edilerek, aktivasyon
engelleri CI-NEB yöntemi kullanılarak analiz edilmiştir. CZO ve Pd-CZO
yüzeylerinin oksijen depolama kapasitesinin La metalinin yüzeye yerleştirilmesi
ile dikkate değer bir artış gösterdiği gözlemlenmiştir. La yerleştirilmiş CZO
yüzeyde gerçekleştirilen CO oksidasyonunun, reaksiyon basamaklarının

vii
aktivasyon engeli içermemesi nedeni ile Pd+La içeren yüzeye göre enerji
bakımından daha avantajlı olduğu bulunmuştur.

Anahtar Kelimeler: Üç Yollu Katalitik Konvertör, Seryum-Zirkonyum Oksit,

Karbon Monoksit Oksidasyonu, Yoğunluk Fonksiyoneli Teorisi, Hesaplamalı
Kimya

viii
 To My Family,
For your endless support and love

ix
 ACKNOWLEDGEMENTS

I wish to offer my sincere thanks and appreciation to my supervisor Prof. Dr. Işık
Önal for his precious help, invaluable suggestions, continuous support, guidance,
criticisms, encouragements and patience throughout this study.

I would like to thank my former and present colleagues Aylin Civan and İlker
Tezsevin for their invaluable help and friendship throughout this study. I am also
thankful to the present and past members of our research group, Dr. Derya
Düzenli, Özgen Yalçın, Özlem Yönder, and Miray Gülbiter.

I would like to thank Fatma Şahin and Elif İrem Şenyurt for their friendship and
all the times we spent together.

Sincerest thanks to my parents Ali and Gönül Kaya for supporting and believing
in me all the way through my academic life.

x
 TABLE OF CONTENTS

ABSTRACT .........................................................................................................v
ÖZ ...................................................................................................................... vii
ACKNOWLEDGEMENTS .................................................................................x
TABLE OF CONTENTS ................................................................................... xi
LIST OF TABLES............................................................................................ xiii
TABLES ........................................................................................................... xiii
LIST OF FIGURES .......................................................................................... xiv
FIGURES ......................................................................................................... xiv
LIST OF ABBREVATIONS ..............................................................................xv
CHAPTERS
1. INTRODUCTION ............................................................................................1
1.1. General Information .....................................................................1
1.2. Three Way Catalyst ......................................................................3
1.3. Air to Fuel Ratio, A/F ...................................................................5
1.4. Catalyst Deactivation....................................................................7
1.5. Computational Chemistry .............................................................8
1.5.1.Schrödinger Equation ..........................................................9
1.5.2. Density Functional Theory ...............................................10
1.5.2.1. The Hohenberg Kohn Theorem ................................10
1.5.2.2. The Kohn and Sham Method ....................................12
1.5.3. Pseudopotentials ...............................................................13
1.6. Objective of the Study ................................................................14
2. LITERATURE REVIEW ...............................................................................15
2.1. Ceria-Zirconia in TWC ...............................................................15
2.2. The Effect of Metal Atom Substitution ......................................16
2.3. Density Functional Theory Studies ............................................20

xi
3. COMPUTATIONAL METHODOLGY ........................................................ 25
3.1. Vienna Ab initio Simulation Package (VASP) .......................... 25
3.2. Simulation Procedure Using VASP ........................................... 26
4. THEORETICAL MODELING OF THREE WAY CATALYST ................. 29
4.1. Bulk Structure Optimization of Cerium-Zirconium Oxide........ 29
4.2. Surface Slab Optimizations ....................................................... 30
4.3.Metal Atom Substitutions to Ce0.75Zr0.25O2 (110) Surfaces ......... 31
4.3.1. Pd Substitution on Ce0.75Zr0.25O2 (110) Surface .............. 32
4.3.2. La Substitution on Ce0.75Zr0.25O2 (110) Surface: .............. 32
4.3.3. Pd+La Substitution on Ce0.75Zr0.25O2 (110) Surface: ....... 33
4.4. Optimization of Gas Phase Molecules ....................................... 34
5. RESULTS AND DISCUSSION .................................................................... 35
5.1. CO Oxidation on La-Ce0.75Zr0.25O2 (110) Surface: .............. 35
5.2. CO Oxidation on Pd+La-Ce0.75Zr0.25O2 (110) Surface: ........ 38
5.3. Oxygen Vacancy Formation Energies of Surfaces .................... 41
6. SUMMARY, CONCLUSIONS AND FUTURE WORK ............................. 43
REFERENCES .................................................................................................. 45
APPENDICES ................................................................................................... 53
APPENDICES
A. SAMPLE INPUT FILES FOR VASP CODE ............................................... 53
A.1. Sample VASP Bodes for Bulk Optimization ............................................. 53
A.1.1. INCAR FILE ........................................................................................... 53
A.1.2. KPOINTS FILE ...................................................................................... 53
A.2. Sample VASP Codes for Surface Optimizations ....................................... 54
A.2.1. INCAR File ............................................................................................. 54
A.2.2. KPOINTS File ........................................................................................ 54
A.3. Sample VASP Codes for CI-NEB Calculations ........................................ 55
A.3.1. INCAR File ............................................................................................. 55
A.3.2. KPOINTS File ........................................................................................ 55

xii
 LIST OF TABLES

TABLES
Table 1.1 Typical composition of exhaust gas for gasoline vehicle (Heck and
Farrauto, 2001) ....................................................................................................... 2
Table 1.2 (a) Emission Standards in the World, (b) Californian emission limits
(Twigg, 2011). ........................................................................................................ 2
Table 1.3 The main reactions in TWC (Wang et al., 2015) ................................... 5
Table 4.1 Energy changes of surfaces due to atomic substitution........................ 33
Table 5.1 CO oxidation on La-Ce0.75Zr0.25O2 surface .......................................... 35
Table 5.2 First step of CO oxidation on Pd-La- Ce0.75Zr0.25O2 Surface ............... 38
Table 5.3 Oxygen vacancy formation of different CZO surfaces. ....................... 42

xiii
 LIST OF FIGURES

FIGURES
Figure 1.1 A diagram of a typical catalytic converter (1), and a metallic
honeycomb (2) (Kaspar, 2003) .............................................................................. 4
Figure 1.2 TWC efficiency for CO, HC and NOx conversions determined by
engine air to fuel ratio............................................................................................ 6
Figure 1.3 Effect of CeO2 content on the surface area stability and dynamic oxygen
storage capacity (at 400 °C) of CZO after calcination. ......................................... 7
Figure 2.1 Catalytic performance of Ce0.2Zr0.8O2 modified of rare earths. ......... 19
Figure 4.1 Optimized bulk (a) CeO2 unit cell, (b) Ce0.75Zr0.25O2 unit cell. ......... 29
Figure 4.2 (a) Top and (b) side view of Ce0.75Zr0.25O2 ........................................ 31
Figure 4.3 Pd doped CZO surface, top and side views, respectively. ................. 32
Figure 4.4 La doped CZO surface top and side views, respectively. .................. 32
Figure 4.5 Both Pd and La doped CZO surface top and side views, respectively.
............................................................................................................................. 33
Figure 4.6 Optimize (a) CO,and (b) CO2 molecule in the gas phase. .................. 34
Figure 5.1 (a) CO molecule in gas phase, (b) CO adsorption on La-Ce0.75Zr0.25O2
Surface ................................................................................................................. 36
Figure 5.2 Desorbed CO2 molecule in gas phase on La-Ce0.75Zr0.25O2 Surface .. 37
Figure 5.3 Relative energy profile of CO Oxidation on La- Ce0.75Zr0.25O2 Surface
............................................................................................................................. 37
Figure 5.4 (a) Gas phase CO and (b) CO adsorption on Pd+La-Ce0.75Zr0.25O2
surface.................................................................................................................. 39
Figure 5.5 Desorption of CO2 molecule from Pd+La-Ce0.75Zr0.25O2 surface. ..... 39
Figure 5.6 Relative energy profile of CO adsorption on Pd+La-CZO surface. .. 40
Figure 5.7 Comparison of first CO oxidation relative energies on La-CZO and
Pd+La-CZO surfaces ........................................................................................... 41

xiv
 LIST OF ABBREVATIONS

A/F Air to Fuel Ratio

CZO Cerium Zirconium Oxide

DFT Density Functional Theory

HC Hydrocarbon

NOx Nitrogen Oxides

OSC Oxygen Storage Capacity

TWC Three Way Catalyst

xv
xvi
 CHAPTER 1

INTRODUCTION

1.1. General Information

Exhaust emissions generated by gasoline motor vehicles are one of the main
sources of air pollution, particularly in urban areas. In a perfect engine, all fuel
reacts with air and is converted to water and carbon dioxide. Nitrogen in the air
would remain unaffected. In reality, the complete combustion of fuel does not
occur in the engine, and therefore carbon monoxide is produced besides unburned
hydrocarbons. Additionally, due to high combustion temperatures, the radical
reactions of nitrogen and oxygen produce several types of nitrogen oxides (Heck
& Farrauto, 2001).

Three main components of exhaust gas are carbon monoxide, CO, partially
burned or unburned hydrocarbons, HCs, nitrogen oxides, NOx, especially NO.
Besides these components, hydrogen, H2, water, H2O, carbon dioxide, CO2,
oxygen, O2, and nitrogen left, N2 etc. are also exhaled by a typical gasoline
engine. The composition of exhaust gas by volume percent of 0.5% CO, 350
ppmv HC, 900 ppmv NOx, and rest is given in Table 1.1. Among these
components, main toxic pollutants are HC, CO and NOx.

1
 Table 1.1 The main composition of exhaust gas for gasoline engines (Heck and
Farrauto, 2001)

Component Concentration
CO 0.5 vol.%
HC 350 ppmv
NOx 900ppmv
H2 0.17 vol.%
H2O 10 vol.%
CO2 10 vol. %
O2 0.5 vol.%

In order to protect the human health and environment, these pollutants have been
restricted in the exhaust gas according to some regulations. In Europa, Euro
Emission Standards are applied; other countries have also their regulations (i.e. in
USA, EPA). Table 1.2 shows EU emission standards for passenger cars (a), and
limitations by historical aspect in California (b).

Table 1.2 (a) Emission Standards in the World, (b) Californian emission limits
(Twigg, 2011).

(a)

2
Table 1.2 Cont.d

(b)

In order to reduce the pollutants from exhaust gas, catalytic converters have been
developed since 1974. Now, the catalytic converters are widely used for the control
of the exhaust emissions of the gasoline vehicles by converting the harmful by-
products CO, NOx, and HC to harmless compounds of H2O, CO2, and O2
(Papavasiliou et al., 2009).

1.2. Three Way Catalyst

To control emission from gasoline vehicles, three way catalysts (TWC) are the
main technology. The TWCs typically consist of;

1. a cordierite (2MgO.2Al2O3.5SiO2) or metal honeycomb monolith

in a stainless steel container,
2. a washcoat with high surface area (alumina),
3. oxygen storage materials (CeO2-ZrO2 ) coated on monolith,
4. the nobel metals such as Pt, Pd, and Rh acting as active phases, and
5. metal oxide as stabilizers and promoters. (Shim et al. 2011; Lucena
et al. 1999; Kaspar et al. 2003)

3
The configuration of typical TWC is given in Figure 1.1. The composition of a
TWC has varied by years depending on the design parameters and cost of the
metals used in the active phase.

Figure 1.1 A diagram of a typical catalytic converter (1), and a metallic

honeycomb (2) (Kaspar, 2003)

The main components of modern TWC are alumina as washcoat (support), ceria-
zirconia, precious group metals (Pt,Pd, Rh) as active phases, various oxides as
stabilizers of alumina surface area, activity promoters, selectivity promoters such
as iron, manganese, calcium, lanthanum, neodymium, and zirconium (Twigg,
2011a).

Three way catalysts includes a lambda or oxygen sensor (λ) to adjust air to fuel
ratio on gasoline engines and operate in a close loop system. The reduction and
oxidation reactions over TWC should be carried out simultaneously for three main
pollutants of CO and HCs and NOx. In this process, CO and HCs are oxidized to
CO2 and H2O while NOx are reduced to N2 (Kaspar, 2003). Main reactions taking
place in TWC can be described as the equations given in Table 1.3. In this table,
the desired products are given, H2O, CO2 and N2. To obtain these products over
the automotive catalyst, the high selectivity of the catalyst is required, because
some other toxic compounds can be produces such as aldehydes and ammonia.

4
 Table 1. 3 The main reactions in TWC (Wang et al., 2015)

Oxidation reactions:
CmHn + O2 → CO2 (CO) + H2O
CO + O2 → CO2
H2 + O2 → H2O
NO reduction reactions:
NO → N2 (N2O, NH3) + H2O + CO2
CO + NO → CO2 + N2 (N2O)
H2 + NO → N2 (N2O, NH3) + H2O
Hydrogen production reactions:
CO + H2O → CO2 + H2
CmHn + H2O → CO2 + H2

1.3. Air to Fuel Ratio, A/F

Air-to-Fuel ratio (A/F) is an important parameter in combustion process.

Stoichiometric value of A/F ratio is 14.7, and only at this value complete
conversion of pollutants can take place and appropriate amount of oxidizing and
reducing agents present in the exhaust gas (Kaspar et al., 2003). In the case of
under the stoichiometric ratio, the fuel is rich, in other words oxygen amount is
insufficient. As a result, the complete oxidation of CO and HCs does not carry
out under stoichiometric ratio due to lack of oxygen. In the lean mode, contrarily,
oxygen content in the exhaust is too high, which causes low NOx conversion
(Gandhi et al., 1976). TWC response to the air/fuel ratio in a typical operation
condition is given in Figure 1.1 (Heck, Farrauto, 2001).

5
 Figure 1.2 TWC efficiency for CO, HC and NOx conversions determined by
engine air to fuel ratio.

Variations between fuel rich and fuel poor (lean burn) conditions cause a decrease
of catalyst performance, since TWSs achieve the simultaneous conversions of CO,
HC, NOx at only the stoichiometric air to fuel point. This phenomenon is due to
the fact that Al2O3 do not store and release oxygen under exhaust gas converter
conditions. In the beginnings of 1980s, CeO2 was found to be promising as oxygen
storage material (Kaspar et al., 1999).

CeO2 improves the dispersion of noble metal, increases the thermal stability of
alumina, promotes CO oxidation by using lattice oxygen, and has high oxygen
storage capacity by storing and releasing oxygen under lean and rich conditions,
respectively (Kaspar et al., 2003).

It is clear that CeO2 in the support layer improves the performance of TWC by
virtue of its high oxygen storage capacity (Kim, 1982).

However pure ceria has weak thermal stability at high exhaust gas temperatures,
it has been gradually changed by the CeO2-ZrO2 mixed oxides in the TWCs
starting from 1995. CeO2 content in CeO2-ZrO2 mixture is an important parameter
for thermal stability and OSC of the catalyst. Figure 1.3 shows the BET surface
area and DOSC as a function of CeO2 mole percent in CZO. As shown in Figure

6
1.3, the optimum composition for the most effective TWC performance is around
60-70 % mol CeO2 compositions (Kaspar et al., 2003).

Figure 1.3 Effect of CeO2 content on the surface area stability and dynamic
oxygen storage capacity (at 400 °C) of CZO after calcination.

The deactivation starts with the increasing temperature, especially after 800°C.
High temperature causes sintering, therefore, surface area of the catalyst and OSC
decreases (Shelef et al., 2002). The solution to this problem is the incorporation of
ZrO2 into the CeO2 lattice. It has been proved that CeO2 is prevented effectively
from sintering (Martinez et al., 2001).

1.4. Catalyst Deactivation

TWCs lose their catalytic properties due to the thermal aging and poisoning. High
operating temperature causes sintering resulting in loss of redox property of
catalyst, metal loss, alloy of noble metal and metal support (Granados et al., 2005;
Fornasiero et al., 2000). Pb, S, P or other elements may cause poisoning of the
catalyst. Coke formation and support pore structure blockage are also the other
cases to cause the catalyst deactivation (Lassi, et al. 2004).

7
1.5. Computational Chemistry

Computational. chemistry is a theoretical approach in solving chemical problems

with the help of computers. Computational methods in chemistry has become a
useful tool to solve complex problems so that researchers can make predictions
before an experimental effort. Thus, it helps researcher save time and money.
Theory of computational chemistry is based on quantum mechanics, classical
mechanics, statistical physics, and thermodynamics.

With the increasing computer power, parallel and grid computing utilities, and
successful numerical techniques, different computations have been efficiently
conducted for chemical and biological modeling. Some of these models are
molecular energies of molecules and structures geometry optimization, bond
energies, reaction energies, reaction pathway, transition states structures and
energies, all thermodynamic properties, vibrational frequencies, atomic charges,
electrostatic potential, magnetic properties and so on (Ramanchandran, Deepa, &
Namboori, 2008). However, computational methods give approximate results with
desired degree of accuracy (Jensen, 2007).

Computational methods can be classified as ab initio methods, semi empirical

calculations, molecular mechanics, molecular dynamics, and density functional
theory (DFT) methods. Choosing a particular computation method depends on
the size of the system, the desired accuracy and the computational facilities
available. For example, for large systems such as proteins can be solved by using
classical mechanics approach called molecular mechanics. In semi-empirical
methods, parameter sets are based on experimental measurements. However,
many molecules such as transition metals does not have sufficiently good
parameter and cannot be treated by these methods with good accuracy.

Ab initio methods use approximation techniques to calculate the wave functions

directly instead of assuming experimental parameters. These methods such as
Hartree-Fock methods can be accurate, but computationally very expensive.

8
The last approach in computational chemistry is density functional theory (DFT).
The computational cost is scaled with the N3 in DFT methods while N4 in Ab
initio methods (N=number of basis set). Therefore, DFT is the most cost effective
method with desired accuracy. DFT methods also account for the electron
correlation; which is neglected in Ab initio methods. Electron correlation is
defined as the difference between the Hartree-Fock energy and the exact solution
of Schrödinger equation. Additionally, many structures such as transition metals
can be treated well compared to other methods. As a result, DFT method is the
most accurate and cost effective method for computational chemistry
(Ramanchandran, Deepa, & Namboori, 2008). The energy accuracy of the
method is between 10 and 40 kj/mol (van Santen and Sautet, 2008). Therefore,
this research study is based on Density functional Theory.

The derivation of DFT method starts with the Schrödinger equation and based on
two theorems of Hohenberg and Kohn (Parr and Yang, 1989). According to
Hohenberg-Kohn theorems, the electronic energy of a system can be modelled
by its electron density. The development of DFT is given by the following part.

1.5.1. Schrödinger Equation

Since probability density of micro-particles or atoms behaves wave-like it needs

a differential equation which describes it, such as a wave function. This equation
was developed by Erwin Schrödinger. The ground state energy of a collection of
atoms may be computed by the time independent, nonrelativistic, Born-
Oppenheimer approximation (1927) (the nuclei are kept fixed) form of
Schrödinger Equation, which is;

̂ ᴪİ (𝑟1 , 𝑟2 , … . , 𝑟𝑁 ) = 𝐸ᴪİ (𝑟1 , 𝑟2 , … . , 𝑟𝑁 )

𝐻 (1. 1)

̂ is Hamiltonian operator, ᴪ
for N-electron atomic or molecular system. Where 𝐻
is wave function of the system, and 𝐸 is enegy. Hamiltonian operator is a sum of

9
the three terms given by

̂ = − 1 ∑𝑁
𝐻 2 ̂ 𝑁
𝑖 ∇𝑖 + 𝑉𝑒𝑥𝑡 + ∑𝑖<𝑗
1
(1. 2)
2 |𝑟𝑖 −𝑟𝑗 |

where first term represents the kinetic energy,

1
𝑇̂ = − ∑𝑁
𝑖 𝛻𝑖
2
(1. 3)
2

𝑉̂𝑒𝑥𝑡 is the external potential operator. External potential is the interaction of the
electrons,𝑍𝛼 , with the atomic nuclei α, which is given by

𝑁 𝑍
𝑉̂𝑒𝑥𝑡 = − ∑𝛼𝑎𝑡 |𝑟 𝛼 (1. 4)
𝑖 −𝑅𝛼 |

and the last term defines the electron-electron interaction Vee,

𝑍𝛼 𝑍
𝑉̂𝑒𝑒 = − ∑𝛼<𝛽 𝛽, (1. 5)
𝑅𝛼𝛽

(Parr and Yang, 1989). The exact solution of Schrödinger equation is only possible
for small systems. Density functional theory (DFT) is an approach for the solution
to Schrödinger equation.

1.5.2. Density Functional Theory

As mentioned before, the Density functional theory is currently the most effective
method to compute the electronic structure of a system and based on two theorems
of Hohenberg and Kohn and later developed by Kohn and Sham.

1.5.2.1. The Hohenberg Kohn Theorem

The main assumption of DFT, which shows that the ground state properties of a
system are unique functionals of the ground state electron density, was proved by

10
Hohenberg and Kohn in 1964. The description of an interacting system of
fermions via its density instead via its many-body wave function is the main idea
of DFT.

Hohenberg and Kohn proposed the following theorem and proved in 1964,

1. Energy functional E[n] can be computed exactly from the ground-state

electron density.
2. Second theorem states that the ground-state electron density can be
calculated exactly using the variational method for minimization of the
Hohenberg-Kohn functional (Ramanchandran, Deepa, & Namboori,
2008).

The total Hamiltonian in more compact form,

̂ = 𝑇̂𝑒 + 𝑉̂𝑒𝑥𝑡 + 𝑉̂𝑒𝑒 .

𝐻 (1. 6)

As stated in the theorem, we can express the total ground state energy in terms
of functionals of the ground state densities 𝜌0 ,

𝐸0 [𝜌0 ] = 𝑇𝑒 [𝜌0 ] + 𝑉𝑒𝑥𝑡 [𝜌0 ] + 𝑉𝑒𝑒 [𝜌0 ] (1. 7)

From the second theorem, the ground-state electron density  (r) determines the
number of electrons N according to the conservation relation

𝑁 = ∫ 𝜌(𝑟)𝑑𝑟 (1. 8)

The minimization condition of energy functional is

𝛿𝐸[𝜌(𝑟)] = 0 (1. 9)

11
These were the first theoretical footings of DFT calculations and they are known
as Hohenberg-Kohn theorems. Other framework, difficult many-body problem of
interacting electrons is simplified to an easier problem of non-interacting electrons
moving in an effective potential, is known as Kohn-Sham DFT (Kohn and Sham,
1965).

1.5.2.2. The Kohn and Sham Method

In the previous method, energy minimization is carried out according to the

changing density. However, kinetic energy calculation from density is not accurate
whereas calculation from wave function is easy and satisfactory. Therefore, Kohn
and Sham combined the wave function and density approach in their method. In
this theory, the effective potential includes the external potential and the Coulomb
interactions between electrons are taken into account. Total energy functional can
be rewritten as

𝐸[𝜌(𝑟)] = 𝑇0 [𝜌] + ∫[𝑉̂𝑒𝑥𝑡 (𝑟) + 𝑈

̂𝑒𝑙 (𝑟)]𝜌(𝑟)𝑑𝑟 + 𝐸𝑥𝑐 [𝜌] (1.10)

where 𝑇0 [𝜌] denotes the kinetic energy of the electrons, but there is no electron-
electron interaction, which is considered as noninteracting system. However,
electron-nuclei interaction is taken into consideration with the Coulomb
interaction between the electrons and Vext accounts for the potential from the
nuclei.

The last term 𝐸𝑥𝑐 [𝜌] is called as exchange-correlation energy. This term takes into
account all other energy contributions that have not been considered by the
previous terms.

However, the modelling of exchange and correlation interactions is very difficult

within the Kohn-Sham method. In order to solve this problem, the local-density
approximation (LDA) was introduce by Kohn and Sham along with their
equations.

12
The LDA suggested that the exchange-correlation energy can be given by
assuming for each infinitesimal element of density, the energy is that of a uniform
electron gas of density. In LDA the exchange correlation functional is based on
the exchange correlation energy xc ( (r)) of a homogeneous electron gas with the

electron density  (r)

𝜌 𝑟 =∫
𝐿𝐷𝐴 [ ( )]
𝐸𝑥𝑐 𝜀 xc (𝜌 (𝑟))𝜌 (𝑟) dr (1.11)

in which the exchange correlation energy solely depends on the local electron
density.

Despite a great success of LDA, this theory is not satisfying all the details of
charge distribution, because charge density is highly non-uniform around atoms.
This problem was solved by introducing the generalized-gradient approximation
(GGA) (Perdew et al., 1992) where the spatial variation in the density is taken into
account. The GGA significantly improved predicted binding and dissociation
energies and here the functional depends on the local electron density as well as
on its first derivative

𝜌 𝑟 =
𝐺𝐺𝐴 [ ( )]
𝐸𝑥𝑐  𝑓 (𝜌 (𝑟), ∇(𝑟))dr (1.12)

Exchange correlation of the system is correlated with both density and derivatives
of density. Thus, more accurate results are obtained with GGA method (Parr and
Yang, 1989; Jensen, 2007; Ramanchandran, Deepa, & Namboori, 2008; van
Santen and Sautet, 2008).

1.5.3. Pseudopotentials

The pseudopotential is a fictional potential that is constructed from the nucleus

and the core electrons. The electronic wavefunctions would be represented
accurately numerous plane waves. A combination of pseudopotentials and fast-
Fourier transforms (FFT) are used to overcome this problem. FFT enables the

13
transformation of the wavefunctions and charge density between real and
reciprocal space. Thus, the calculation scale of the problem take place in two
different spaces, and therefore they are carried out in the ‘cheaper’ space.

1.6. Objective of the Study

It is well known that rare earth dopant enhances the thermal stability and OSC of
CZO catalyst as stated in the literature. However, in the view of the literature
findings, the reaction mechanisms and the electronic effect of these improvement
are unclear. Additionally, there has been little study on the investigation of the
effect of La doping on catalytic activity. Furthermore, there is no theoretical study
in the open literature on La doped CZO catalyst. To that end, the main objective
of this theoretical study is to investigate CO oxidation in La and Pd+La doped
TWC system by using DFT methods of computational chemistry. For this purpose,
Vienna Ab initio simulation Package is used for the computer application of DFT
methods. La and Pd+La doped ceria-zirconia catalyst surfaces are prepared. Then,
these surfaces are investigated for CO oxidation reactions. Relative energy profiles
and activation barriers of CO adsorption and desorption reactions steps on these
surfaces are obtained and compared. Promotional effect of La doping is
investigated. Thus, with the help of the results of this study, novel TWC
configurations may be determined for catalytic performance before experimental
research.

14
 CHAPTER 2

LITERATURE REVIEW

Since the early 1990s, ceria-zirconia mixed oxides has been used in the TWCs
instead of pure ceria due to pure ceria’s poor thermal instability. The insertion of
zirconia (ZrO2) in ceria (CeO2 enhances the thermal stability, surface area and
oxygen storage capacity of the catalyst (Kaspar et al., 1999). Ceria-zirconia system
also shows better redox properties than that of pure zirconia because of higher
defect sites leading to increase in oxygen vacancy generation (Damyanova et al.,
2007).

Different compositions of Ceria-Zirconia (CeO2-ZrO2) automotive catalysts

combined with other metal atom substitutions and promoters have been
investigated by many researchers in terms of their catalytic activity and stability.

2.1. Ceria-Zirconia in TWC

The CeO2-ZrO2 solid solutions impregnated on γ- Al2O3 is investigated by by Di

Monte et al. (2000). They proved the positive effect of impregnation of γ- Al2O3
with cerium-zirconium on the oxygen storage capacity even after calcination.

Kaspar et al. (2002) synthesized different compositions of CexZr1-xO2 using citrate

complexation method to investigate the effect of ZrO2 content on textural and
structural properties of CZO solid solutions. They suggested that cerium rich
compositions can be good candidates for catalytic applications at low to medium
temperature.

15
NO reduction by CO over Pd-Al2O3 and Pd-Ce0.6Zr0.4O2/Al2O3 catalyst was
studied by Di Monte et al. (2002) to investigate the effects of Ce0.6Zr0.4O2 addition
to Pd-Al2O3 catalyst. They pointed out that the Ce0.6Zr0.4O2 addition strongly
affects the surface Pd species under reaction conditions. The activity of catalyst is
improved below 500 K; catalytic activity is not affected by support above 500 K;
and oxidized Pd species are stabilized at catalytic surface. In the case of zirconia
addition, due to the direct interaction of Pd species with oxygen species of the
support, CO removal rate is promoted by these oxygen species. The removal of
surface adsorbed CO/NO species is observed more easily compared to zirconia
absent catalyst.

Gayen et al. (2006) investigated the activity of Rh-Pt catalysts for TWC. It is
observed that main synergistic effect is caused by Rh3+ ion reduction at lower
temperature in the presence of Pt2+ ions. Bimetallic catalysts show better
performance in the oxidation of CO, and NO and C2H4 reduction improved
compared to the monometallic catalysts.

2.2. The Effect of Metal Atom Substitution

The effect of metal atom substitution to CeO2-ZrO2 catalyst has been investigated
by many researchers. Early studies on the effect of rare earth dopants were on
Pd/Al2O3 catalyst.

XPS and TPR studies were carried out by Muraki et al. (2001) to investigate the
catalytic effects of La2O3 on Pd/Al2O3 catalyst for the NO reduction. They
observed that NO reduction enhances with the addition of lanthana. As a result of
XPS and TPR studies, hydrocarbon chemisorption and therefore catalyst
poisoning are suppressed by the addition of lanthana.

16
The previous work of Muraki et al. (1986) also indicates that the reduction of NO
is inhibited by hydrocarbons on Pd-La2O3/Al2O3 catalyst. In the presence of
La2O3, NO reduction was better compared to Pd-only catalyst. This may occur due
to the weakening adsorption strength of HCs with the Pd-La cooperation. NO
reduction by H2 is observed as highly selective and fast.

Yao et al. (2011) also explained the positive catalytic effect of the addition of
La2O3 to the Pd-based catalyst C3H8 conversion after aging. They found that Pd
dispersion and reducibility are higher than that of the La2O3 absent catalyst.

Another investigation on the effect of La2O3 addition to the catalytic activity of

Pd-Al2O3 catalyst was conducted by Kim et al. (2000). They prepared Pd-
La2O3/Al2O3 catalyst by co-impregnation, and Pd/La2O3/Al2O3 catalyst by
sequential impregnation, methods. The co-impregnated catalyst had better light-
off performance than that of the catalyst prepared by the sequential impregnation.
Although Pd-La2O3/Al2O3 lost its surface area after thermal aging, it conserved its
superior activity. As a promoter La2O3 improves the thermal stability of Pd-
La2O3/Al2O3 catalyst through the close interaction with Pd during thermal aging
while suppresses the relation between PdO and alumina. However, in the case of
Pd/La2O3/Al2O3 catalyst, lanthana interacts with the alumina during the thermal
aging and stabilizes the support.

Skoglundh et al. (1996) compared Pd alone and La doped Pd-alumina catalyst in

terms of light-off performance and redox properties. They observed that the
addition of La widen the interval compared to Pd alone catalyst under reducing
conditions. Additionally, NO conversion is improved by the addition of
lanthanum. They explained that better NO conversion is as a result of the
formation of Pd-La oxide or alloy which favors the reduction reaction of NO by
CO instead of the reaction between CO and O2.

17
NO chemisorption on the Pd (100) surface with ultra-thin over layers of La2O3 and
Al2O3 was studied by Logan and Graham (1989). NO was partial dissociation of
NO was observed on La2O3 over layers whereas it is nondissociative on Al2O3
over layers at 300 K, which suggests that La contributes to dissociative adsorption
of NO on Pd (100) surface.

With the replacement of alumina catalyst with ceria-zirconia catalyst, the effect of
rare earth dopants on CZO have been started to be investigated in detail.
Additionally, it is known that the performance of Pd in CZO catalyst can be
improved by introduction of a promoter (Wang et al., 2015). The effect of the
introduction of La2O3 to Pd based catalyst on the catalytic activity has also been
studied various researches by experimentally.

Vidmar et al. (1997) studied the OSC of Ce0.6Zr0.4O2 catalyst doped with three
valent cations such as La, Nd, and Y. OSC of the doped system at low temperature
is improved by 30% compared to undoped catalyst. They also observed that all
dopants stabilize CeO2 with respect to high temperature calcination. Surface La
content increases with the calcination with respect to bulk La concentration.

A series of Ce0.2Zr0.8O2 catalyst containing different amount of La have been

prepared by Wang et al. (2010). In their experimental research, the effect of La
content in CZO on the catalytic activity was investigated. They observed that La
content contributes to conversion of all target compounds on the aged catalysts
and fresh samples are successful on NO reduction.

Another important study was also carried out by Wang et al. (2011). In this study,
a series of Ce0.2Zr0.8O2 (CZO) doped with rare earth metals of La, Nd, Pr, Sm, and
Y were prepared and their characterization were carried out. The metal atom
doping effect on OSC and thermal stability of the solid solution were investigated.
The catalytic performance over a wide air to fuel operating window were also
examined. The major findings of this study are summarized in Figure 2.1.

18
It is reported that the presence of La, Nd and Pr improves the thermal stability of
CZO catalyst. It also improves the reducibility.

Figure 2.1 Catalytic performance of Ce0.2Zr0.8O2 modified of rare earths.

Due to increased metal support interaction, relatively higher three-way catalytic

activity is observed for all of the target pollutants.

In a later study of the research same group, Wang et al. (2011), the effect of rare
earth (La, Nd, Pr, Sm, and Y) addition to C0.2Zr0.8O2 and Pd based C0.2Zr0.8O2
catalyst was investigated. They observed that the stability, reducibility and metal-
support interaction of CZO catalyst increase in the presence of rare earth metal
leading to higher catalytic performance for all target pollutants. The air to fuel
ratio window increases with increasing dynamic oxygen storage capacity.

19
Zhao et al. (2013) also studied C0.67Zr0.33O2-x catalyst to investigate the effect of
catalytic activity of rare earth modification. For this reason, Ce-Zr-M (M=. La, Pr,
Nd, Sm, and Y) ternary mixed oxides were prepared and used as support. Since
ceria is rich in the support, the cubic structure is featured in the structure as
observed from XRD results. The incorporation of rare earth metal into ceria-
zirconia improves the oxygen storage capacity and the interaction between PdO
species and support. The main reason of this increase is due to the relatively higher
concentration of Ce3+ species on the catalyst surface with the addition of rare earth
metal. Superior activity for NOx and HC conversion is observed after aging
treatment, especially for the catalyst containing Pr or Nd.

Guo et al. (2007) investigated the effect of La2O3 on the performance of Pd/ceria-
zirconia catalyst. In this experimental study, CexZr 1-xO2 nanoparticles (x = 0.75,
0.62) were prepared. The activity of Pd-only three-way catalyst was tested in the
fixed-bed reactor. The composition of simulated exhaust gas is 3% CO, 5000 ppm
C3H8, 5000 ppm NO, 10% CO2, O2 and N2 gases. They found that the light-off
performance of the catalyst is decreased by the addition of La2O3. However, the
oscillation of the conversion of NO and HCs are suppressed. After the aging of
catalyst, the operating window turned to lean burn.

These experimental studies address that the interaction between lanthanum and the
support material enhances the activity of TWC catalyst.

2.3. Density Functional Theory Studies

There has recently been great interest in theoretical studies with the increased
computer capacity and development in DFT techniques over last decades. Recent
DFT studies on the development of CZO catalyst with regard to CO oxidation are
summarized below.

Fe-modified CeO2 (111) surface is studied to investigate the mechanisms for the
CO oxidation by Chen and Chang (2011). They used periodic density functional

20
theory corrected for the on-site Coulomb interaction by a Hubbard term (DFT+U).
They observed that Fe is stable both as an adsorbed atom on the surface and as a
dopant in the surface region. Oxygen vacancy formation is facilitated by dopant
Fe atoms, while Fe adatoms might suppress oxygen vacancy formation.
Physisorbed CO2 and chemisorbed CO (carbonate) species are observed on the Fe
doped CeO2 (111) surface, whereas, on the clean surface, only physisorbed CO is
observed.

Another DFT+U study was performed by Wang et. al (2009) to investigate the
effect of Zr doping on the oxygen storage properties of several Ce1-xZrxO2 surfaces
(x=0.75, 0.50, 0.25). They found that bond energies of Zr-O species increase with
the increasing amount of Zr. However, relaxation energies follow a parabolic
profile with a minimum value for for the catalyst of x=0.5. Vacancy formation by
decomposing it into two terms: the bond energy and relaxation energy. They
concluded that the relaxation energy is more dominant parameter than bond
energy; therefore, equimolar Ce and Zr concentration in CZO catalyst exhibit the
highest oxygen storage capacity.

Nolan et al. (2005b) studied the lattice parameter of bulk ceria using DFT methods
implemented on VASP. The computed lattice parameter is 5.470 Å, which is
consistent with the experimental value of 5.411 Å. They also investigated the
relative stability and oxygen vacancy formation energy of (111), (110) and (100)
surfaces (Nolan et. al, 2005a). The surface stability is in the order of (111)> (110)
> (100), whereas the (110) ceria surface has the lowest vacancy formation energy
and therefore the most reactive surface.

Introduction of noble metals such as Pd, Pt and Rh to ceria catalyst is also studied
by several researches with DFT methods.

Pd doped ceria (111) surface was investigated by Yang et al. (2007) by DFT
method implemented in VASP. PAW method and GGA approximation is used. Pd

21
atom is adsorbed on different surface sites. It is observed that Ce-O bridge position
in these sites is most favorable.

Gerceker and Önal (2013) investigated CeO2 and Ce0.75Zr0.25O2 surfaces with the
modification by Pd4 and Rh4 metal clusters adsorption and Pd and Rh substitution
in terms of CO oxidation mechanisms. DFT are used to model the surfaces and
reaction mechanisms with the help of computer program VASP based on PAW
method and GGA approximation. Oxygen vacancy formation energy was
calculated as 43.7 kcal/mol for Pd substituted CZO surface. On this surface the
activation barrier is reported 45 kcal/mol between the steps of first CO adsorption
and desorption of CO2.

CO oxidation on Mn doped ceria (111) surface was studied by Hsu et al. (2012).
They compared the activation barrier of CO2 desorption for Mn adatom and Mn
atom substituted surfaces. On the Mn atom substituted surface, no CO2 desorbs
creating oxygen vacancy with no activation barrier, whereas Mn adatom Mn
adatoms restricts the vacancy formation energy and the activation barrier is
calculated as 0.84 eV.

Civan (2014) studied the effect of CO oxidation mechanisms on Mn doped

Ce0.75Zr0.25O2 (110) surfaces. For this purpose, Mn, Mn-Pd, and Mn-Rh doped
surfaces was prepared. According to relative energy profile calculations, Mn-Pd
doped surface is found to be energetically most favored. The activation barrier of
CO2 desorption step is overcome with the incorporation of Mn and Pd on this
surface.

Yeriskin and Nolan (2009) investigated the effect of lanthanum doping on CO

adsorption at La-doped Ceria (111) and (110) surfaces using DFT+U method. It is
observed that La3+-O- defect state forms with doping with La3+ at both (111) and
(110) surfaces. At the undoped (111) surface, CO only weakly physisorbs, while
strong adsorption of CO is observed at doped surface resulted in direct CO2
formation.

22
Formation of monodentate or bidentate carbonate species depends on the oxygen
vacancies on doped (110) surfaces. At (110) and (111) surfaces, CO interaction
with the surface is improved over the corresponding undoped surfaces. It is
observed that the theoretical findings are consistent with experimental results, and
also the results obtained from other dopants in ceria.

In another study of the same authors (2010), they point out that oxygen vacancy
formation energy is reduced with the substitution of lanthanum. Energy
requirement for the formation of an oxygen vacancy in La-doped structure is at
least 0.90 eV on (111) surface and 0.64 eV on (110) surface. It is seen that these
values are small enough and vacancy formation will be enhanced compared to the
undoped surfaces. As a result, they concluded that La-doping of ceria surfaces
shows enhanced reactivity over the undoped surfaces.

Experimental and theoretical studies suggest that metal atom substitution enhances
the catalytic activity of CZO catalyst. To that end, in this study, the effect of La
doping on the catalytic activity of ceria-zirconia catalyst has been investigated.
Comparison of the activities of La and Pd doped CZO surfaces in terms of CO
oxidation has been carried out.

23
24
 CHAPTER 3

COMPUTATIONAL METHODOLGY

In this research study, Density Functional Theory methods are implemented in

Vienna Ab initio Simulation Package (VASP). Starting with the bulk structure
optimization of support material, two different surface planes are cleaved from the
bulk with required depth and these surfaces are also optimized. Then, metal atom
substitutions on these surfaces are carried out. The catalytic performances of the
surfaces in terms of CO oxidation are investigated on these surfaces. For this
purpose, gas phase reactants are optimized and proposed reaction mechanism steps
are modelled. CI-NEB method is used to predict activation barriers of the reaction
steps.

3.1. Vienna Ab initio Simulation Package (VASP)

There are quite a number of computational software packages that use methods of
theoretical chemistry to calculate structures and properties of molecules and
solids. In this study, quantum mechanical calculations are implemented in Vienna
ab Initio Simulation Package (VASP) code, (Kresse and Fürthmüler 1996; Kresse
and Hafner 1993), based on DFT formalism.

The computational procedure of the VASP code includes an iterative solution of

the Kohn–Sham equations based on residuum-minimization and optimized
charge-density mixing routines. The total energy is optimized with respect to the
positions of the atoms within unit cell or supercell. The electron exchange and
correlation are treated within the generalized gradient approximation (GGA),
(Perdew, & Chevary, 1992), using projector augmented approximations (PAW)

25
method (Blöch 1994; Kresse, & Joubert, 1999). VASP code employs DFT method
in a periodic manner. Specifically, the code gives more accurate results for solid
systems, such as metal oxides, that have periodic boundary conditions.

To perform VASP code, several input information of the system are required.
These are initial positions of the atoms, pseudopotentials, specified k-points mesh
values and keywords for convergence.

Depending on the given input information, the outputs of VASP are several:
energy and force, volume, density of states, charges, optimized geometry of the
structure, vibrational frequency, and so on. The program performs the minimum
energy optimization. The key parameters determining the convergence of VASP
are the number of basis functions (plane wave cutoff) and the number of k- points
(k-spacing).

3.2. Simulation Procedure Using VASP

In this study, DFT simulation of CO oxidation on Ce0.75Zr0.25O2 (110) surfaces

are carried out in VASP code using the generalized gradient approximation (GGA)
and projector augmented-wave (PAW) method.

In the computations, Mankhorst-Pack k-point mesh is selected (19x19x19) for

bulk optimizations, (4x4x1) for surface optimizations, and (1x1x1) for gas phase
molecules optimizations (Monkhorst and Pack, 1976) in order to determine the
integration points. In structural optimizations, convergence criterion is determined
as 0.015eV/Å for the net force acting on each atom. Energy cut-off is set to 500eV
for the calculations.

First, the optimization of bulk CeO2 is performed using lattice parameter reported
in the literature. After obtaining the optimized lattice parameters, CeO2 bulk is
created and cleaved for CeO2 (110) surface with the depth of 6 atomic layers as a
(3x2) supercell.15 Å vacuum space is added on top of the surface to avoid any

26
interaction with the periodically continuing upper layers. The bottom layer is kept
fixed to describe the bulk structure while others are fully relaxed.

Ce0.75Zr0.25O2 stoichiometry is obtained by replacing one of the Ce atoms in each

layer with a Zr atom. La and Pd atom substitutions are carried out in the same way;
one or two Ce atoms on the top layer were exchanged with La and Pd atoms and
then further optimized. Similarly, at the bottom layer, atoms are kept fixed to
represent of a bulk structure of catalyst surface while the atoms in remaining layers
were fully relaxed.

After the optimization of surface models, CO adsorption and desorption were

computed on these optimized surfaces. Gas phase CO reactant and CO2 product
molecules are optimized in a 10Å x 10Å x 10Å vacuum cell. Relative energy of
each reaction step is calculated with the following equation

𝐸𝑟𝑒𝑙=𝐸𝑠𝑦𝑠𝑡𝑒𝑚 − (𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒+ Σ𝐸𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) (3.1)

where 𝐸𝑠𝑦𝑠𝑡𝑒𝑚 is the energy of the overall molecular system, 𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒 is the
optimized surface energy and Σ𝐸𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 are energies of the optimized gas phase
reactants.

Activaiton barrier calculation for a reaction, Climbing Image Nudged Elastic Band
method (CI-NEB) is used (Henkelman et al., 2000). This method finds the saddle
point and minimum energy paths between known initial and final steps of the
reaction. After creating a specified number of images with equal distances from
each other, these intermediate images are optimized. The structure with the highest
energy is considered as the transition state structure. Consequently, the
approximate activation barrier energy of the reaction is obtained by using the
energy of transition structure. The transition state structure are optimized again to
verify that it is a first order saddle point. Sample input scripts used in the
computations are given in Appendix A.

27
28
 CHAPTER 4

THEORETICAL MODELING OF THREE WAY CATALYST

4.1. Bulk Structure Optimization of Cerium-Zirconium Oxide

Cerium oxide is a rare earth oxide having fluorite type structure with space group
Fm3m. It contains cubic closed-packed metal atoms with oxygen atoms placed in
all tetrahedral holes (Trovarelli, 1996). Experimental value of lattice parameter of
CeO2 crystal is 5.411 Å (Trovarelli, 1996). The oxygen - oxygen distance is 2.705
Å, which is half the lattice parameter. Ce-Ce and Ce-O bond lengths are 3.86 and
2.36 Å, respectively.

Modelling of TWC starts with the optimization of cerium oxide (CeO2) unit cell.
Lattice parameter of CeO2 is computed as 5.464 Å which is consistent with the
experimental value.

(a) (b)
Figure 4.1 Optimized bulk (a) CeO2 unit cell, (b) Ce0.75Zr0.25O2 unit cell.

29
Cerium-zirconium oxide is obtained in the stoichiometric ratio Ce0.75Zr0.25O2
(CZO) by replacing one out of four Ce atoms in the unit cell of CeO2 with one
zirconium atom. Ce0.75Zr0.25O2 unit cell lattice parameter is computed as 5.379
Å, which is also consistent with the experimental value of 5.39 Å (Yang et al.,
2009). The decrease of the CZO unit cell size is due to the surface strain caused
by substitution of zirconium substitution (Wang et al., 2009). CeO2 and
Ce0.75Zr0.25O2 unit cells are shown in Figure 4.1.

In models, Ce atom is represented by gray ball, Zr blue, Pd pink, La orange, carbon

yellow, and oxygen red.

4.2. Surface Slab Optimizations

The surface energy quantifies the energy loss for disruption of chemical bonds that
occur when a crystal is cleaved and a surface is created. It is calculated per unit
area of a surface as the difference between the energy of the system terminated by
the surfaces (slab) and the system of the same number of unit cells within the bulk.

Slabs used in ab initio calculations have finite thickness, which has to be chosen
large enough, so that the surface energy reaches its convergence level.

As the results of calculation on different surfaces, the (111) surface is found as

energetically the most stable surface followed by (110) and (310) surfaces, and
accordingly less reactive. In other words, (110) and (310) surfaces make more
reactive catalyst (Alessandro Trovarelli, Paolo Fornasiero). Therefore, in this
study, (110) surface is used in the computations cleaving from bulk Ceria with 6
atomic layers. Then, the (110) ceria surface is doped with zirconia. The optimized
surfaces are sown in Figure 4.2.

30
 (a) (b)
Figure 4.2 (a) Top and (b) side view of Ce0.75Zr0.25O2

4.3. Metal Atom Substitutions to Ce0.75Zr0.25O2 (110) Surfaces

Single metal atom of La and both Pd and La are substituted on Ce0.75Zr0.25O2

(110) surface to investigate the catalytic activity of rare earth metal. The surfaces
are obtained by replacing cerium atom at the top layer with dopant atom.

After the metal introduction to the catalyst surface, energy change of each
surface due to metal atom substitution is calculated using the following equation

∆𝑬𝒔𝒖𝒃𝒔𝒕𝒊𝒕𝒖𝒕𝒊𝒐𝒏 = 𝑬𝑴−𝒔𝒖𝒓𝒇 + 𝑬𝑪𝒆 − (𝑬𝒔𝒖𝒓𝒇 + 𝑬𝑴 ) (4. 1)

where, 𝐸𝑀−𝑠𝑢𝑟𝑓 is the energy of the surface doped with a metal atom, 𝐸𝑠𝑢𝑟𝑓 the
energy of undoped surface, 𝐸𝐶𝑒 and 𝐸𝑀 are the energies of single cerium atom and
the dopant metal atom, respectively. The single atoms are also optimized in a
vacuum cell.

31
4.3.1. Pd Substitution on Ce0.75Zr0.25O2 (110) Surface

Pd doped CZO surface is prepared by positioning Pd and Zr atoms aligned with

each other. To obtain this configuration, one cerium atom at the top layer with a
Pd atom is replaced with one Ce atom. Figure 4.3 depicts top and side views of
Pd-CZO (110) surface.

,
Figure 4.3 Pd doped CZO surface, top and side views, respectively.

4.3.2. La Substitution on Ce0.75Zr0.25O2 (110) Surface:

Lanthanum doped surface is prepared in the same way of Pd doped CZO

surface. La and Zr are aligned with each other on the surface. In this case,
one cerium atom is replaced with a La atom at the top layer. Top and side
view of optimized La-CZO (110) surface is given in Figure 4.4.

Figure 4.4 La doped CZO surface top and side views, respectively.

32
4.3.3. Pd+La Substitution on Ce0.75Zr0.25O2 (110) Surface:

In this case, bimetallic doped catalyst surface is prepared. For this reason, CZO
(110) surface doped with both Pd and La atom by replacing with two cerium atoms
on the upmost surface. As shown in Figure 4.5, Pd, Zr and La atoms are diagonally
positioned over the surface.

Figure 4.5 Both Pd and La doped CZO surface top and side views, respectively.

In the doping process, to remove and substitute another atom requires energy. To
calculate the energy changes of metal substituted surfaces with respect to bare
CZO surface, Eq. 4.1 is used and results are listed in Table 4.1.

Table 4.1 Energy changes of surfaces due to atomic substitution

Surface Energy change (kcal/mol)

Pd-CZO (Gerceker, 2013)
295.514
La-CZO
63.14701
Pd-La-CZO
361.1463

Experimental studies revealed that La introduction into CZO lattice is facile

(Wang et al., 2010), which is verified by current study with DFT computations.
The minimum energy changes is observed in the case of La atom substitution on
CZO surface, which is 63.147 kcal/mol. Since La has a similar atomic radius to

33
that of Ce atom, its substitution does not require high energy compared to Pd
substitution (295.514 kcal/mol). However, bi-metallic substitution requires more
energy and may be the most difficult one. As a result, La substitution is
energetically more favorable than those of Pd and bimetallic substitution.

4.4. Optimization of Gas Phase Molecules

In CO oxidation reaction, CO is reactant and CO2 is product. Their energies are

required in the calculation of relative energies. The gas phase CO and CO2
molecules are optimized in a 20Å×20Å×20Å vacuum cell and gas phase formation
energies are calculated. Optimize CO and CO2 molecules are given in Figure 4.6.

(a) (b)

Figure 4.6 Optimized (a) CO, and (b) CO2 molecule in the gas phase.

C-O bond length is calculated as 1.14Å and 1.18Å in CO and CO2 molecules,
respectively. Calculated gas phase energies are -340.34 kcal/mol (-14.79 eV) and
-528.7 kcal/mol (-22.99 eV) for CO and CO2 molecules, respectively.

34
 CHAPTER 5

RESULTS AND DISCUSSION

In this phase of the study, CO oxidation reaction steps and energetics on the
optimized CZO surface models are investigated. The results obtained in this part
are compared with the previously reported findings of Pd substituted Ce0.75Zr0.25O2
(110) (Gerçeker and Onal, 2013) and Mn doped Ce0.75Zr0.25O2 (110) (Civan, 2014)
surfaces in terms of CO oxidation.

5.1. CO Oxidation on La-Ce0.75Zr0.25O2 (110) Surface:

To investigate the catalytic activity of atomic lanthanum doped Ce0.75Zr0.25O2

(110) surface in terms of CO conversion, one cerium atom on the CZO surface is
replaced by a palladium atom. On the La-CZO surface, dopant lanthanum atom
and zirconium atom of the top layer are aligned.

Energies of CO adsorption and CO2 desorption steps are calculated relative to

bare La-CZO surface energy. Reaction steps and relative energies of CO
oxidation mechanism on La-Ce0.75Zr0.25O2 surface are given in Table 5.1.

Table 5.1 CO oxidation on La-Ce0.75Zr0.25O2 surface

Reaction Step Relative Energy

(kcal/mol)
R1: CO(g)  CO(ads) -86.967
-
53.363
R2: CO(ads) + OlatCO2(g)

35
The first step of CO oxidation reaction begins with the approaching of a gas phase
CO molecule to the surface. CO strongly interacts with the surface and it is
adsorbed as carbonatelike species shown in Figure 5.1. It is bound on Ce-O bridge
position next to the palladium atom creating carbonate species on the surface. To
form this adsorption configuration, carbon atom pulls two oxygen atoms out of the
CZO surface. The C-O bond lengths of the adsorbed CO molecule were found to
be 1.317 Å on the ceria side and 1.331 Å on La side. Optimized gas phase CO
approaching to the surface and adsorbed CO on the surface are shown in Figure
5.1. The adsorption step is exothermic with the approximate energy of -86
kcal/mol.

Figure 5.1 (a) CO molecule in gas phase, (b) CO adsorption on La-Ce0.75Zr0.25O2

Surface

CO2 is then released to gas phase with the labelled step R2 creating oxygen
vacancy on the surface. Figure 5.2 shows CO2 desorption step and the surface
oxygen vacancy.

36
 Figure 5.2 Desorbed CO2 molecule in gas phase on La-Ce0.75Zr0.25O2 Surface

Relative energy profile of first CO Oxidation on La-CZO surface is given in Figure

5.3. Approximately 30 kcal/mol energy required for the CO2 desorption step.
However, there is no activation barrier is observed at the CO2 desorption step
according to CI-NEB analysis. Oxygen vacancy formation energy is calculated as
34.49 kcal/mol.

Figure 5.3 Relative energy profile of CO Oxidation on La- Ce0.75Zr0.25O2

Surface

37
As reported in the study of Gerceker and Önal (2013), an activation barrier of 45
kcal/mole for CO2 desorption step on the Pd- Ce0.75Zr0.25O2 surface is calculated.
As a result of current study, by means of doping CZO surface with La, activation
barrier for CO2 desorption has been overcome.

5.2. CO Oxidation on Pd+La-Ce0.75Zr0.25O2 (110) Surface:

To investigate the contribution of La doping to the catalytic activity of Pd-CZO

catalyst in terms of CO oxidation, Pd+La-Ce0.75Zr0.25O2 (110) surface is prepared.
One cerium atom is replaced by a palladium atom, and the other cerium atom
diagonal to the palladium atom is replaced by one lanthanum atom on the CZO
surface. Energies of each step are calculated relative to Pd+La-Ce0.75Zr0.25O2
surface energy. CO adsorption and CO2 desorption reaction steps and
corresponding relative energies on Pd+La-CZO surface are given in Table 5.2.

Table 5.2 First step of CO oxidation on Pd+La- Ce0.75Zr0.25O2 Surface

Reaction Step Relative Energy

(kcal/mol)
R1: CO(g)  CO(ads) -125.036
-96.687
R2: CO(ads) + Olat CO2(g)

CO oxidation on the surface begins with approaching gas phase CO molecule to

the surface. CO molecule is absorbed exothermically at the Ce-O bridge site next
to the palladium atom as shown in Figure 5.4, this step is labelled as R1 and it is
highly exothermic with the energy of -125 kcal/mol. Length of carbon-oxygen
bond is 1.36 Å in both sides. Optimized geometries of CO molecule approaching
the surface, and adsorbed molecule are shown in Figure 5.4.

38
 Figure 5.4 (a) Gas phase CO and (b) CO adsorption on Pd+La-Ce0.75Zr0.25O2
surface.

Then, CO molecule desorbs from the surface forming CO2 molecule to the gas
phase. At this step, one of the surface oxygen atoms is pulled off by C atom and
surface oxygen vacancy is created. CO2 is then released to gas phase creating an
oxygen vacancy. This step requires approximately 30 kcal/mol energy. The
vacancy formation energy is computed as exothermic with a negative value of -
4.30 kcal/mole at this surface. Desorption of CO2 from the surface and oxygen
vacant surface are shown in Figure 5.5.

Figure 5.5 Desorption of CO2 molecule from Pd+La-Ce0.75Zr0.25O2 surface.

39
Relative energy profile of CO adsorption on Pd+La-CZO surface is shown in
Figure 5.6. At the CO2 desorption step, CI-NEB analysis is carried out for the
activation barrier analysis. At this step, the high activation barrier is observed.
According to experimental study of Guo et al. (2007), the lanthanum doping
decreases the performance of Pd-CZO catalyst. This experimental phenomenon is
verified by theoretically in this study. However, as reported in the same study, NO
reduction enhances in the case of La doping. Therefore, further theoretical study
is needed to explain the electronic effect of La contribution to NO reduction.

Figure 5.6 Relative energy profile of CO adsorption on Pd+La-CZO surface.

The relative energy profiles of both La-CZO and Pd+La-CZO surfaces are given
in Figure 5.7. As shown in this figure, CO adsorption step is more exothermic on
Pd+La-CZO surface compared to Pd absent surface while desorption requires
almost same amount of energy.

40
 La-CZO

CO2 des.
Pd+La-CZO

CO ads.

Figure 5.7 Comparison of first CO oxidation relative energies on La-CZO and

Pd+La-CZO surfaces

According to CI-NEB analysis, La doped CZO surface becomes prominent

compared to bimetallic substituted surface due to the lack of activation barrier at
CO2 desorption step. However, in Civan’s study (2014), the synergistic effect of
Pd and Mn was observed in terems of CO oxidation mechanism on Pd-surface.
According to experimental studies conducting on Pd-CZO surface, La contribution
enhances the NO and HC conversion while suppress the CO conversion (Wang et
al., (2009, 2010, 2011); Guo et al. (2009)). On the other hand, at the La doped
CeO2 (110) surface, the interaction of CO with the surface is increased on La doped
surfaces compared to the undoped surface. In this respect, in the light of findings
of literature and current study, this research points out that La only doped surface
may be a promising candidate for TWC.

5.3. Oxygen Vacancy Formation Energies of Surfaces

In this part, oxygen vacancy formation energies of La-Ce0.75Zr0.25O2 and Pd-La-

Ce0.75Zr0.25O2 are investigated. For this reason, one oxygen atom is removed from
the surface. Oxygen vacancy formation energy 𝐸𝑣𝑎𝑐 is calculated by the following
expression

41
 1
𝐸𝑣𝑎𝑐 = (𝐸𝑣𝑎𝑐+𝑠𝑢𝑟𝑓𝑎𝑐𝑒 + 𝐸𝑂2 ) − 𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒 (5.1)
2

where 𝐸𝑣𝑎𝑐+𝑠𝑢𝑟𝑓𝑎𝑐𝑒 is the energy of oxygen vacant surface, i.e. surface after CO2
desorption; 𝐸𝑠𝑢𝑟𝑓𝑎𝑐𝑒 is the energy of clean catalyst surface; 𝐸𝑂2 is the energy of
oxygen molecule in the gas phase.

Oxygen vacancy formation energies of CZO catalyst surfaces with different

dopant atoms are given in Table 5.3. Vacancy formation energy is calculated as
34.49 kcal/mol for La-CZO and a negative value of -4.30 kcal/mole for Pd+La-
CZO surface. Oxygen vacancy formation energy on Pd-CZO (110) was computed
as 43.7 kcal/mole (Gerçeker and Önal, 2013).

Incorporation of both Pd and Mn in CZO (110) surface was studied by Civan

(2015). The oxygen vacancy formation energy was obtained as -12.09 kcal/mol
for Mn doped Pd-CZO surface while 59.83 in the absence of Pd substitution.

Table 5.3 Oxygen vacancy formation of different CZO surfaces.

Oxygen Vacancy formation

Surfaces energy, kcal/mol
Pd-CZO (Gerceker, 2013) 43.69
La-CZO (current study) 34.49
Pd+La-CZO (current study) -4.30
Mn-CZO (Civan, 2014) 59.83
Mn+Pd-CZO (Civan, 2014) -12.09

As reported in Table 5.3, the lowest vacancy formation energy is of Mn+Pd doped
CZO surface. It is followed by Pd+La doped CZO surface. The synergism between
metal dopant and Pd atom enhances the oxygen vacancy formation of the catalyst.

42
 CHAPTER 6

SUMMARY, CONCLUSIONS AND FUTURE WORK

In this thesis, catalytic properties of automotive exhaust emission catalysts

containing Pd and Pd+La on ceria-zirconia have been investigated by quantum
mechanical approach. For this reason, ceria-zirconia (110) surface was prepared
and top layer of this surface is doped with atomic La and Pd+La atoms. The effect
of La doping and synergetic effect of noble and rare earth metal doping were
investigated in terms of catalytic activity. For this reason, CO oxidation reaction
was studied on these surfaces. Concluding remarks according to the results are
summarized as follows:

Since lanthanum is in the same group with cerium, its substitution on the ceria
surfaces is energetically more favorable than the palladium substitution.

The formation energy of lanthanum doped CZO (110) surface is lower than that
of the palladium doped CZO (110) surface. Lanthanum improves the oxygen
vacancy formation property of Pd-doped surface.

CO adsorption on both lanthanum and palladium doped CZO (110) surfaces more
exothermic than that of the La only doped CZO surface. It might be due to the
improvement of the oxygen storage capacity of Pd+La-CZO surface as a result of
a structural deformation caused by bimetallic doping.

As a result of DFT computations La doped CZO catalyst shows better performance

by eliminating the activation barrier at the desorption step compared to Pd-CZO
catalyst (Gerceker and Onal, 2013). In the case of bimetallic doping, desorption
43
step may be carried out very slow or impossible due to high activation barrier at
this step. Previously conducted experimental findings reports that the light of
performance of Pd-CZO catalyst is decreased by the addition of La to the catalyst.
It may be explained that CO conversion is suppressed due to the activation barrier
observed in the desorption step obtained in this theoretical study.

It can be concluded that surface geometry and substitutional doping play a crucial
role in determining the reactivity of ceria-zirconia surfaces to the first step in CO
oxidation.

As a next step of this study, the research on NOx reduction should be studied on
La and Pd+La doped CZO surfaces. With the experimental knowledge that La
improves the NOx reduction properties of Pd based catalyst (Wang et al, 2009),
and NOx reduction should be considered on the doped CZO surfaces.

44
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51
52
 APPENDICES

APPENDIX A

SAMPLE INPUT FILES FOR VASP CODE

A.1. Sample VASP Bodes for Bulk Optimization

A.1.1. INCAR FILE

SYSTEM = CeO2
!ISTART = 0
PREC = HIGH
ISIF = 3
IBRION = 1;
NSW = 150
LREAL = AUTO
ISMEAR = 0; SIGMA = 0.01;
ENCUT = 500
ALGO = FAST
EDIFFG = -0.001

A.1.2. KPOINTS FILE

K-Points
0
Monkhorst Pack
18 18 18
0 0 0

53
A.2. Sample VASP Codes for Surface Optimizations

A.2.1. INCAR File

EDIFFG = -0.015

IBRION = 2
!POTIM = 0.2;
!NFREE = 20

ISMEAR = 0; SIGMA = 0.01;

LREAL = Auto
ENCUT = 500
IDIPOL = 3

LDIPOL = .TRUE.
NSW = 300

ALGO=FAST

A.2.2. KPOINTS File

K-Points
0
Monkhorst Pack
4 4 1
0 0 0

54
A.3. Sample VASP Codes for CI-NEB Calculations

A.3.1. INCAR File

!FOR CI-NEB
IMAGES = 8
SPRING = -5
ICHAIN = 0
LCLIMB = .TRUE.
LTANGENTOLD = .FALSE.
LDNEB = .FALSE.
!EDIFFG = -0.015

IBRION = 1;
POTIM = 0.2;
!NFREE = 20

NSW = 500
LDIPOL = .TRUE.

ISMEAR = 0; SIGMA = 0.1;

LREAL = Auto
ENCUT = 500
IDIPOL = 3

LCHARG = .FALSE.
ALGO=FAST

A.3.2. KPOINTS File

K-Points
0
Monkhorst Pack
4 4 1
0 0 0

55