SYNTHESIS, PROPERTIES AND APPLICATIONS OF TiO2

NANOPARTICLES

Assignment II
By

MEGHNA MOHANDAS
MOHAMMED FAZIL BIN ZAKARIA
MUHAMMED RAJOOL
M V HARISANKAR

DEPARTMENT OF CHEMICAL ENGINEERING

Government Engineering College,
Thrissur, Kerala
Synthesis of TiO2 Nanoparticle

TiO2 nanoparticles in a variety of forms, including nanotubes, nanofibers, nanosheets,

nanorods, and linked architecture, have been created. The synthesis techniques that are
frequently used are oxidation, sol-gel, solvothermal, hydrothermal, and thermal
decomposition. TiO2 can also be synthesised by other techniques, such as sol, electrode
position, sonochemical and microwave-assisted, micelle and inverse micellar techniques.

1. Hydrothermal Method:
Tri-titanate nanotubes easily formed from the anatase phase of the starting material at
140 ∘C when various compositions and particle sizes of TiO2 mixed powders were
subjected to hydrothermal reaction in the presence of NaOH, and tri-titanate belts and
plates formed from the rutile phase component at 170 ∘C. Typically, the hydrothermal
synthetic technique is carried out in steel pressure vessels, or autoclaves with Teflon
liners, at controlled temperatures and pressures.

2. Sol-Gel Technique:
The sol–gel synthesis approach provides the benefit of improved purity and
uniformity of the produced nanoparticles at low temperatures and is typically used to
create crystalline or amorphous structures of organic or inorganic materials. After a
TiO2 precursor was hydrolyzed, nano-TiO2 were created using the sol–gel method.
Acid-mediated titanium (IV) alkoxide hydrolysis typically leads to this, and a
condensation reaction follows.

3. Solvothermal Method:
The hydrothermal approach and the solvothermal synthetic strategy are similar, with
the exception that the former uses non-aqueous solvents. The working temperatures in
the former can be significantly higher than in the latter due to the employment of a
wide variety of organic solvents with noticeably high boiling points. Intriguing
benefits of the solvothermal approach also include enhanced shape, particle size, and
crystallinity of the produced nanoparticles, as well as temperature and pressure
controls of the solvents utilised in the synthesis. Furthermore, this technique offers a
flexible path for producing TiO2 nanoparticles with enhanced dispersity and a
restricted size distribution. TiO2 nanorods and nanoparticles were prepared using the
solvothermal synthetic approach, either with or without surfactant mediation.

4. Chemical and Physical Vapour Deposition Method:

The condensation of materials from the vapour phase into the solid phase is known as
vapour deposition. The method is known as chemical vapour deposition (CVD) if
there isn't a chemical reaction occurring in the vacuum chamber, or as physical vapour
 deposition (PVD). The deposition reaction in a conventional CVD method is fueled
by thermal energy, which warms the gases inside the coating chamber. Using a liquid
precursor and TTIP pyrolysis in an oxygen/helium environment, TiO2 nanoparticles
with typical diameters less than 10 nm were effectively created.

5. Thermal Decomposition method

Over the last ten years, a number of researchers have used the thermal decomposition
approach to synthesise TiO2 nanoparticles. TiO2 nanoparticles, for example, were
produced when TTIP vapour was thermally degraded at 300 °C. In a saturator, the
TTIP vapour and the saturated carrier gas—dry, particle-free, and deoxidized
nitrogen—were heated outside. It was shown that the heterogeneous breakdown of the
TTIP was the initial step in the creation of fine TiO2 nanoparticles.

6. Oxidation method
In order to create the nanoparticles, this method directly oxidises the element titanium
through the application of oxidants or anodic processes. For example, well-aligned
TiO2 nanotubes were generated successfully employing a voltage of 10–20 V and
0.5% hydrogen fluoride [87]. To obtain the nanotubes, the titanium anodized plate had
to be annealed for six hours at 500 °C in the presence of oxygen. It was found that
adjusting the applied voltage allowed for control over the nanotubes' diameter and
length.

Properties of TiO2 Nanoparticles

1. Crystalline Properties
Nanocrystalline TiO2 exists in three major polymorphic forms: rutile, anatase, and
brookite. This classification is based on the conditions of fabrication and post
fabrication heat treatment. There also exists a fourth polymorphic form TiO2 (B),
which is quite uncommon. Both the anatase and rutile phases possess tetragonal
crystal structures even though they do not belong to the same phase groups, while
brookite has an orthorhombic structure and the uncommon TiO2(B) phase is
monoclinic. The rutile phase is less stable than the anatase phase at 0 K. Anatase
phase TiO2 is opted for solar cell application over other phases, due to its low
density, high electron mobility, and low dielectric constant. As a result of its low
density, anatase phase easily undergoes transition to the rutile phase at high
temperatures (usually around 450–1200 ∘C).

2. Optical Properties
TiO2 nanoparticles are prized for their optical properties, including durability, visible
light transparency, and stability in water. Structural factors like phase composition and
size affect their behaviour. As particle size decreases, TiO2 shifts from opaque to
 transparent, even blocking UV light. Anatase TiO2 displays superior catalytic ability
and electron mobility, beneficial for solar and photocatalytic applications, thanks to its
low oxygen adsorption and higher hydroxylation degree. Rutile TiO2, with its high
refractive index, finds use in optical communication devices.
Under UV light, TiO2 nanoparticles generate electrons and holes, with anatase
proving more effective due to its ability to absorb UV light and produce charge
carriers. Rutile is less efficient due to bulk recombination of electrons and holes. TiO2
nanoparticles are seen as near-ideal photocatalysts due to their selective oxidation
properties, prompting further research into nano-sized TiO2-based photocatalysts.

3. Electrochemical Properties
TiO2 nanoparticles exhibit semiconductor behaviour with a wide band gap. The band
gap varies depending on the crystal phase, with rutile, anatase, and brookite phases
having different energy band gaps. Anatase phase, for example, has a smaller electron
effective mass than rutile, leading to higher mobility for charge carriers. The
conduction band (CB) consists of 3d orbitals of titanium, while the valence band (VB)
involves 2p oxygen orbitals hybridise with 3d titanium orbitals.
The properties of the lattice oxygen sites play a crucial role in the superhydrophilicity
of TiO2 nanoparticles. Interaction of trapped h+ ions with lattice oxygen weakens the
oxygen ions and titanium bonds, facilitating the interruption of these bonds by water
molecules. This interruption generates -OH groups on the surface, leading to
superhydrophilicity.

​ One disadvantage of TiO2 nanoparticles in photoelectrochemical devices is the large

density of states involved in electron-hole recombination and electron transfer
reactions at the electrolyte-oxide interface. However, this property can be
advantageous for the adsorption of redox-active compounds, such as serum proteins
like fibrinogen. Fibrinogen can chemisorb onto TiO2 nanoparticle surfaces through an
electron transfer process. The electronic behaviour of TiO2 nanoparticles affects the
thrombogenicity of fibrinogen, as the band structure of fibrinogen interacts with that
of TiO2 nanoparticles.

Applications

Titanium dioxide (TiO2) nanoparticles have a wide range of applications in various

engineering fields due to their unique properties. Here are some key applications:

1. Photocatalysis:
TiO2 nanoparticles are extensively used in photocatalytic reactions to degrade organic
pollutants in water and air. When exposed to ultraviolet (UV) light, TiO2
nanoparticles generate electron-hole pairs, which can react with organic compounds,
breaking them down into harmless byproducts.
2. Self-cleaning surfaces:
TiO2 nanoparticles are incorporated into coatings and paints to create self-cleaning
surfaces. When exposed to sunlight, the photocatalytic activity of TiO2 nanoparticles
helps break down organic dirt and microbial contaminants, keeping the surface clean.

3. UV protection:
TiO2 nanoparticles are used in sunscreen formulations to provide UV protection.
They scatter and absorb UV radiation, preventing it from penetrating the skin and
causing damage.

4. Antibacterial applications:
TiO2 nanoparticles exhibit antibacterial properties due to their ability to generate
reactive oxygen species under UV light exposure. This property is utilised in various
applications such as antibacterial coatings for medical devices, textiles, and food
packaging materials.

5. Dye-sensitised solar cells (DSSCs):

TiO2 nanoparticles are a key component in DSSCs, which are a type of
third-generation solar cell. In DSSCs, TiO2 nanoparticles serve as the semiconductor
material that absorbs photons and generates electron-hole pairs, initiating the flow of
current and producing electricity.

6. Gas sensors:
TiO2 nanoparticles are used in gas sensors for detecting various gases such as
hydrogen, methane, and volatile organic compounds. The high surface area and
reactivity of TiO2 nanoparticles enable efficient gas adsorption and detection.

7. Optoelectronic devices:
TiO2 nanoparticles are utilised in optoelectronic devices such as photovoltaic devices,
light-emitting diodes (LEDs), and sensors due to their excellent optical and electrical
properties.

8. Water purification:
TiO2 nanoparticles are employed in water treatment processes for disinfection and
removal of contaminants. Their photocatalytic activity enables the degradation of
organic pollutants and inactivation of microorganisms present in water.

Overall, the unique properties of TiO2 nanoparticles make them valuable materials in
various engineering applications ranging from environmental remediation to energy
production and healthcare.