IN232

Term Paper
Ankur Bhaumik
18895

Titania or Titanium Dioxide (TiO2)

Introduction [and Motivation] – Titania is one of the most widely studied oxides of transition
metal. It has many interesting physical and chemical properties. As the demand for cleaner
fuels has increased, so has the interest of chemists in titania. It is widely studied as a potential
water-splitting photocatalyst that can generate hydrogen from water.

Crystal structure and lattice

It crystallises in four distinct polymorphs: rutile (tetragonal, space group P42/mnm), anatase
(tetragonal, space group I41/amd), brookite (orthorhombic, space group Pbca) in order of
decreasing abundance. Of these forms, rutile TiO2 is the most stable.i For the rest of the paper,
only rutile has been explored.

ii
Figure 1 Crystal structures of TiO2 : (a) anatase, (b) rutile, and (c) brookite
The primitive unit cell of rutile contains two formula units of TiO2, with a formula of Ti2O4. Each
Ti atom is surrounded by a slightly distorted octahedron of O atoms.

Lattice Constants
a=b= 4.59 A˚
c=2.95 A˚
α=β=γ=90◦

Figure 2 Primitive Unit Cell of Rutile TiO2

The physical properties of TiO2 not only depend on the phase structure but also depends on
the agglomerated microstructure, pores, and particle size. For different physical and chemical
processes like charge transfer, chemical reaction, photon absorption, etc., the molecules on
the surface of particles are more active than those staying inside.

For a primitive tetragonal lattice, all h,k, and l values are allowed for the XRD pattern. The XRD
pattern shown below was taken for nano-sized TiO2 samples, and thus there is a low signal-to-
noise ratio. Therefore, peaks with lower intensities are not observed.

Figure 3 XRD Pattern of Rutile TiO2iii

2θ Miller Indices
27.42 110
36.08 200
41.25 111
44.20 220
56.51 002
63.44 301
Phonon Dispersion

Figure 4 Phonon Dispersion Curve of Rutile TiO2iv

As mentioned previously, TiO2 effectively has six atoms in its unit cell (2 Ti and 4 O). Thus, we
expect 18 phonon modes since we must account for all three directions. As expected, 3 of
these modes are acoustic, and the rest are optical. The acoustic phonons modes are not
degenerate at the Γ points, indicating that the vibrations along the three orthogonal axes are
not similar. At most other points, they are degenerate.
The acoustic and optical modes are separated but not very much, which can be explained by
the fact that Ti (48 u) and O (16 u) atoms have different but not significantly different masses.

Brillouin Zone

Figure 5 1st Brillouin Zone of Rutile TiO2v

As expected, the 1st Brillouin zone of a primitive tetragonal lattice is also

primitive tetragonal.

Electronic Properties
Undoped titanium dioxide is an intrinsic, n-type semiconductor because of the oxygen
vacancies in the TiO2 lattice. The oxygen vacancies act as electron donors.
 Figure 6 Electronic Band Diagram of rutile TiO2vi

The above electron band diagram was calculated using DFT. The direct band gap (Γ to Γ) was
calculated to be 3.1 eV, close to the experimentally observed value of 3.05 eV. The indirect
band gap (Γ to R) was calculated to be 2.95 eV.vii
TiO2 as a photocatalyst.
When light falls on a semiconductor, it creates e/h pairs that, if created near the surface, can
oxidise/ reduce the chemical species in the surrounding environment. e-h pairs can quickly
recombine with each other. Thus, most semiconductors show little photocatalytic activity.
What makes TiO2 different is that its band structure is such that it exhibits charge carrier
trappingviii, i.e., holes tend to get trapped at the surface, and electrons tend to get trapped in
the bulk of the material. Thus, most photocatalytic applications of TiO2 involve nanostructures
with a greater surface area-to-volume ratio.
Ideally, a photocatalyst should be active in the visible region, so sunlight can be directly used.
However, TiO2 has a band gap that falls in the UV region. Thus, researchers are working on
reducing its band gap without affecting (or improving) its photocatalytic ability by doping etc.
Other Applications
1. As a white pigment as it does not absorb in the visible region.
2. As a UV-blocking agent in sunscreen.
References

i F. Labat, P. Baranek, C. Domain, C. Minot, and C. Adamo: J. Chem. Phys. 126 (2007) 154703.
ii
Godbert, Nicolas & Mastropietro, Teresa & Poerio, Teresa. (2018). Mesoporous TiO2 Thin
Films: State of the Art. 10.5772/intechopen.74244.
iii I M Joni et al 2018 J. Phys.: Conf. Ser. 1080 012042
iv
Lan, Tian et al (2015). Phonon quarticity induced by changes in phonon-tracked hybridization
during lattice expansion, and its stabilization of rutile TiO$_2$. Physical Review B. 92.
10.1103/PhysRevB.92.054304.
v
Barreda, Jose et al. (2013). Pressure-induced phase-transition sequence in CoF2: An
experimental and first-principles study on the crystal, vibrational, and electronic properties.
Physical Review B. 88. 214108. 10.1103/PhysRevB.88.214108.
vi Chinedu, E. Ekuma and Diola Bagayoko. Ab-initio Electronic and Structural Properties of
Rutile Titanium Dioxide
vii Chinedu, E. Ekuma and Diola Bagayoko. Ab-initio Electronic and Structural Properties of
Rutile Titanium Dioxide
viii Jenny Schneider et al. Understanding TiO2 Photocatalysis: Mechanisms and Materials