Hanoi university of sciences, VNU

Topic:
DENSITY FUNCTIONAL STUDIES ON ABSORPTION OF
TITANIUM DIOXIDE ON CARBON NANOTUBES

Student: Nguyen Thi Trang, K57 International Physics

Supervisor: Dr. Nguyen Tien Cuong.

Hanoi, 6- 2015

CONTENTS
I. Introduction
1.1.Carbon nanotubes
1.2. Titanium dioxide (TiO2)n
1.3. Absorption of titanium dioxide on carbon nanotubes
II. Results and discussions
2.1 Geometric optimization
2.2 Molecular orbital
III. Conclusion
IV. References
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CARBON NANOTUBES
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What is carbon nanotubes (CNTs)?

Figure 1 : CNTs

CNTs are fullerene-related structures which consist of

graphene cylinders closed at either end with caps containing
pentagonal rings.
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CARBON NANOTUBES
Types of CNTs

Figure 2: Single Wall CNT (SWNT)

Figure 3: Multiple Wall CNT (MWNT)

Can be metallic or semiconducting depending on their

geometry.

CARBON NANOTUBES
History of CNTs
1952, L. V. Radushkevich and V. M. Lukyanovich
50 nm MWCNT Published in Soviet Journal of Physical Chemistry
1991-1992, Sumio Lijima
discovers MWCNT in arc burned rods Mintmire, Dunlap, and Whites
predict amazing electronic and physical properties
1993, Bethune and Iijima independently discover SWCNT

CARBON NANOTUBES
SWNTs
CNT: Rolling-up a graphene sheet to form a tube

Figure 4: Schematic of a CNT

Figure 5: Image of CNT

CARBON NANOTUBES
Types of SWNTs

Figure 5: Types of SWNTs

CARBON NANOTUBES
Properties
Properties depending on how it is rolled up.
If the nanotube structure is armchair then the
electrical properties are metallic (n=m)
If the nanotube structure is chiral then the
electrical properties can be either semiconducting
with a very small band gap, otherwise the
nanotube is a moderate semiconductor.
In theory, metallic nanotubes can carry an
electrical current density of 4109 A/cm2 which is
more than 1,000 times greater than metals such as
copper
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TITANIUM DIOXE (TiO2)n

(TiO2)n
Titanium dioxide, also known as titanium (IV) oxide or titania, is
the naturally occurring oxide of titanium, chemical formula TiO2.
There are 3 types of TiO2 crystals: rutile, anatase, brookite

Figure 6: Types of (TiO2 )n

TITANIUM DIOXIDE (TiO2)n

Application of titanium dioxide
water and air
purification

TiO2
Material for
photocatalyst
Fresh air
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ABSORPTION OF (TiO2)n ON CNTs

- TiO2 : absorb only the
wavelength smaller than 400
nm (UV) very good.
- CNT: absorb the wavelength
from 400 to 760 nm (Visible
light) better than UV region
- TiO2 / CNT system : absorb
both of UV and visible regions
good due to the additional CNT

Figure 7 : UVvis spectra

of TiO2

11 5
Minh Thuy Nguyen, et al, Adv. Nat. Sci.: Nanosci. Nanotechnol.

ABSORPTION OF (TiO2)n ON CNTs

Hoffmann Mechanism
When (TiO2)n/CNT adsorbed
UV light (high energy), hole
and electron are generated
in TiO2, then electron is
transferred to CNT, hence
electron-hole recombination
rate reduced
Hoffmann M.R. , et al, Chem. Rev. 95
(1995) 69-96

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ABSORPTION OF (TiO2)n ON CNTs

Wang Mechanism

Wang W. D. , et al, J. Mol. Catal. A Chem 223

(2005) 194-199

When (TiO2)n/CNT adsorbed

visible light (low energy),
hole
and
electron
are
generated in CNT, then both
of them is transferred to
TiO2.
electron: O2 O2hole
: OH OH+
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ABSORPTION OF (TiO2)n ON CNTs

Aims of the research
Density functional calculations have performed to investigate the
absorption of (TiO2)n clusters on CNT, for:
1/ Understanding the role of CNT and TiO2 in the enhanced photocatalytic activity of TiO2/CNT system
2/ Explaining the Hoffmann and Wang mechanisms

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RESULTS AND DISCUSSION

Computational details
- All calculations were carried out using Dmol3 package (Material studio
6.0) within the framework of DFT.
- The GGA-PBE was adopted for exchange-correlation potential.
- For all atoms, electron-core interaction are described by ultrasoft
pseudo-potentials.
- A cutoff energy of 380eV and regular Monkhorst Pack grid of 2x2x4 kpoints were used

DFT
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RESULTS AND DISCUSSION

Geometric optimization

(TiO2)n clusters

Table 1 : Anatase (TiO2)n clusters

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RESULTS AND DISCUSSION

Geometric optimization

SWNT (10,0)

SWNT (10,0) 3x1x1 super-cell

C-C bonding length =1.426

Vacuum slab = 15

Figure 8: SWNT (10,0) system

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RESULTS AND DISCUSSION

Geometric optimization

In progress

Figure 9: (TiO2)n / SWNT systems

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RESULTS AND DISCUSSION

Molecular orbitals

TiO2 1a configuration

TiO2 Anion
When TiO2 gains
one
electron,
the
additional
electron density is localized
around Ti atom

TiO2 Cation
In opposite, when TiO2 loses
one electron, the reduced
electron density is caused by
Oxygen atoms
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RESULTS AND DISCUSSION

Molecular orbitals

(TiO2)2 2a configuration

(TiO2 )2 Anion
The additional electron density is
localized around Ti atom

(TiO2)2 Cation
The reduced electron density
is caused by Oxygen atoms
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RESULTS AND DISCUSSION

Molecular orbitals

(TiO2)2 2b configuration

(TiO2 )2 Anion
The additional electron density is
localized around Ti atom

(TiO2)2 Cation
The reduced electron density
is caused by Oxygen atoms
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RESULTS AND DISCUSSION

Electron configuration
Ti has 22 electrons
2s

2p 3s

3p 3d 4s

2s

2p

Oxygen has 8 electrons

1s

1s

- The additional electron density is localized around Ti atom due to

3d-orbitals
- The reduced electron density is caused by Oxygen atoms by 2p-

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CONCLUSIONS
Density functional calculations have performed to investigate the absorption of
(TiO2)n clusters on CNT for understanding the role of CNT and TiO2 in the
enhanced photo-catalytic activity of TiO2/CNT system, and explaining the
Hoffmann and Wang mechanism.
The geometric optimizations of (TiO2)n cluster with (n=1,2) as well as SWNT
(10,0) 3x1x1 super-cell have been successfully calculated. The results show 1a,
2b, and 2c are stable configurations.
The molecular orbital are also calculated for 1a, 2b, and 2c TiO 2 atom, TiO2
Anion, and TiO2 Cations. It is found that when an TiO2 atom gains one electron,
the electron tend to occupy 3d orbitals of Ti. So the additional electron density is
localized around Ti atom due to 3d orbitals. In opposite, the reduced electron
density is caused by Oxygen atoms by 2p orbitals contribution
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FUTURE WORKS
Geometric optimize TiO2/CNT systems
Calculate adsorption energy
Calculate charge population, charge transfer, and electron
density deformation
Calculate band structure DOS, and PDOS

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